JP2018034488A - Decorative film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film having excellent scratch resistance and a high gloss value, and a method for producing the same.SOLUTION: A decorative film 1a includes a polyvinyl chloride resin layer 20 and a colorless transparent coating layer 10. The coating layer 10 is formed of a cured product of an ultraviolet-curable resin composition containing a polymerization initiator having an acylphosphine oxide group represented by chemical formula (A). Preferably, the polyvinyl chloride resin layer 20 contains a non-phthalate plasticizer.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative film and a manufacturing method thereof.

Conventionally, a decorative film is used by being attached to a fitting such as a building or furniture for the purpose of surface protection or decoration. As such a decorative film, a polyvinyl chloride (PVC) film, a polyethylene terephthalate (PET) film, and the like are known.

A coating layer may be provided on the surface of the decorative film in order to improve scratch resistance and impart gloss. For example, a film in which a PET film coated with an ultraviolet resin is bonded to a PVC film using an adhesive is known. Moreover, as a prior art regarding the coating to a film, what was disclosed by patent document 1, 2, for example is known. In Patent Document 1, a polyvinyl chloride sheet or the like is used as a medium on which a photocurable ink composition for inkjet printing having a specific composition is applied. Patent Document 2 discloses a hard coat film including a base film such as a polyvinyl chloride resin and a hard coat layer formed from a coating liquid containing a specific material.

JP-A-2015-168723 Japanese Patent Laying-Open No. 2015-203770

The film obtained by laminating the PET film and the PVC film as described above has room for improvement in terms of cost and flexibility due to the PET film. Then, this inventor examined forming a coating layer directly on a PVC film using ultraviolet curing resin in order to make use of the flexibility of a PVC film. However, since the PVC film is deteriorated by heat due to ultraviolet irradiation, the coating layer cannot be irradiated with sufficient ultraviolet rays, and the curing of the ultraviolet curable resin does not sufficiently proceed, and the resulting film has scratch resistance. It turns out that there is a problem. Further, since the ultraviolet curable resin was not sufficiently cured, the surface of the obtained film was not uniform, and the obtained film did not have sufficient gloss.

This invention is made | formed in view of the said present condition, By suppressing the fracture | rupture by the thermal deterioration of a PVC film, the decorative film which is excellent in abrasion resistance and has a high gloss value, and its manufacturing method are provided. It is for the purpose.

The inventors of the present invention have made various studies on a decorative film having excellent scratch resistance and a high gloss value. And, when forming the coating layer, by using a polymerization initiator having an acylphosphine oxide group, it is possible to reduce the cumulative exposure amount of ultraviolet rays and to suppress deterioration of the polyvinyl chloride resin layer due to heat. The present invention has been completed by finding out what can be done.

The decorative film of the present invention has a polyvinyl chloride resin layer and a colorless and transparent coating layer, and the coating layer includes a polymerization initiator having an acylphosphine oxide group represented by the following chemical formula (A). It consists of the hardened | cured material of the ultraviolet curable resin composition containing.

The polymerization initiator is preferably a compound represented by the following chemical formula (A-1).

（上記化学式（Ａ−１）中、Ｒ^１、Ｒ^２２及びＲ^３２は各々独立に炭素数６〜２０の芳香族基を表し、Ｒ^２１及びＲ^３１は各々独立に−ＣＯ−基又は単結合を表す。）

(In the chemical formula (A-1), R ¹ , R ²² and R ³² each independently represents an aromatic group having 6 to 20 carbon atoms, and R ²¹ and R ³¹ each independently represent a —CO— group or a single bond. Represents.)

The polymerization initiator is preferably at least one of compounds represented by the following chemical formulas (A-11) and (A-12).

The polyvinyl chloride resin layer preferably contains a non-phthalic acid plasticizer.

The coating layer preferably has a thickness of 3 μm to 15 μm.

The polyvinyl chloride resin layer preferably has a thickness of 80 μm to 200 μm.

The coating layer preferably has a gloss value of 90 or more.

The decorative film further includes a pressure-sensitive adhesive layer and a release film or release paper, and the coating layer, the polyvinyl chloride resin layer, the pressure-sensitive adhesive layer, and the release film or It is preferable that release papers are laminated in order from the surface.

The method for producing a decorative film according to the present invention is a method for coating a polyvinyl chloride resin layer with an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group represented by the following chemical formula (A). And a coating layer forming step of forming a coating layer by curing the ultraviolet curable resin composition by ultraviolet irradiation.

The method for producing the decorative film preferably includes a lamination step of laminating a polyethylene terephthalate resin layer on the polyvinyl chloride resin layer before the coating layer forming step.

The present invention can provide a decorative film having excellent scratch resistance and a high gloss value, and a method for producing the decorative film.

It is the cross-sectional schematic diagram which showed an example of the decoration film of this invention which has an adhesive layer. It is the cross-sectional schematic diagram which showed an example of the decoration film of this invention which has a polyethylene terephthalate resin layer.

[Decoration film]
The decorative film of the present invention has a polyvinyl chloride resin layer and a colorless and transparent coating layer, and the coating layer includes a polymerization initiator having an acylphosphine oxide group represented by the following chemical formula (A). It consists of the hardened | cured material of the ultraviolet curable resin composition containing.

<Polyvinyl chloride resin layer>
The decorative film of the present invention has a polyvinyl chloride resin layer containing a polyvinyl chloride resin. Since the polyvinyl chloride resin has flexibility, the decorative film of the present invention has good elongation.

The polyvinyl chloride resin layer preferably has a thickness of 80 μm to 200 μm, and more preferably 140 μm to 200 μm. By setting it as such an aspect, the softness | flexibility and breaking strength of a decoration film can be raised more.

The polyvinyl chloride resin layer preferably contains a plasticizer, and more preferably contains a non-phthalic acid plasticizer. Further, as long as it does not impair the effects of the present invention, if necessary, it contains additives such as stabilizers, ultraviolet absorbers, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents. Also good. As these additives, those generally used for polyvinyl chloride resins can be used.

<< Polyvinyl chloride resin >>
Examples of the polyvinyl chloride resin contained in the polyvinyl chloride resin layer of the present invention include a vinyl chloride homopolymer, and a copolymer of vinyl chloride with another monomer copolymerizable with vinyl chloride. Can be mentioned. Examples of other copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; methyl (meth) acrylate, ethyl (meth) acrylate, and the like. (Meth) acrylic acid alkyl ester; maleic acid diester such as dibutyl maleate and diethyl maleate; fumaric acid diester such as dibutyl fumarate and diethyl fumarate; vinyl cyanide such as acrylonitrile and methacrylonitrile; vinylidene chloride, bromide Examples thereof include vinyl halides such as vinyl; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more. In the present specification, “(meth) acrylic acid” represents “at least one of acrylic acid and methacrylic acid”.

The content of the other copolymerizable monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. The polyvinyl chloride resin contained in the polyvinyl chloride resin layer of the present invention is preferably a vinyl chloride homopolymer from the viewpoint of excellent dimensional stability.

The average degree of polymerization of the polyvinyl chloride resin is preferably 800 to 1200. By setting it as such an aspect, workability can be improved and especially workability can be improved by combining with the below-mentioned plasticizer. In the present invention, the average degree of polymerization of the polyvinyl chloride resin means the average degree of polymerization measured according to JIS K 6721 “Testing method for vinyl chloride resin”.

<< Plasticizer >>
The decorative film of the present invention preferably contains a plasticizer. The plasticizer is not particularly limited as long as it can easily process the film. As the plasticizer, those usually used in the field of films can be used. For example, diphthalic diester such as dioctyl phthalate (di-2-ethylhexyl phthalate), dibutyl phthalate, dinonyl phthalate, diisononyl phthalate (DINP), dioctyl adipate, dioctyl sebacate, etc. Examples include phosphoric acid triesters such as acid diesters, tricresyl phosphate, and trioctyl phosphate, epoxy plasticizers such as epoxidized soybean oil and epoxy resins, and polyester plasticizers.

The polyvinyl chloride resin layer preferably contains a non-phthalic acid plasticizer as a plasticizer. By using a non-phthalic acid plasticizer, the scratch resistance can be further enhanced. As the non-phthalic acid plasticizer, a polyester plasticizer is preferably used.

The polyester plasticizer has good compatibility with the polyvinyl chloride resin. In addition, compared with phthalic acid plasticizers generally used as plasticizers for polyvinyl chloride resins, polyester plasticizers have a high molecular weight and are therefore difficult to dissolve and swell in solvents. Therefore, by using a polyester plasticizer, the solvent resistance can be improved while imparting flexibility to the polyvinyl chloride resin layer.

The polyester plasticizer is, for example, a method of directly polycondensing a dibasic acid or an anhydride thereof with a dihydric alcohol, or a lower alkyl ester such as a methyl ester or an ethyl ester of a dibasic acid and a dihydric alcohol. It can be produced by a method of performing a transesterification reaction or the like.

Examples of the dibasic acid or anhydride thereof include adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. The said dibasic acid or its anhydride may be used independently, and may mix 2 or more types.

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, and the like.

Especially, it is preferable that the said polyester plasticizer is an adipic acid polyester plasticizer. Adipic acid polyester plasticizers can be suitably used because of their high compatibility with polyvinyl chloride resins. The adipic acid polyester plasticizer is a reaction product of adipic acid and one or more dihydric alcohols.

The number average molecular weight of the polyester plasticizer is preferably 2000 or more. When the number average molecular weight of the polyester plasticizer is less than 2000, the polyester plasticizer tends to dissolve and swell in the solvent, and the solvent resistance may be insufficient. A more preferable lower limit of the number average molecular weight of the polyester plasticizer is 2500.

The number average molecular weight of the polyester plasticizer is preferably 3500 or less. When the number average molecular weight of the polyester plasticizer exceeds 3500, the solvent resistance is improved, but the entanglement of the polymer chain becomes strong. The film forming property may be increased and the film formability may be reduced. Moreover, when the shearing force is increased, heat is generated during film formation, and the polyvinyl chloride resin may be decomposed, which may reduce the heat resistance of the polyvinyl chloride resin layer. Furthermore, since the melt viscosity becomes high, the flowability of the molten resin is lowered, and a flow mark is generated, and the appearance of the polyvinyl chloride resin layer may be deteriorated such as a rough surface. A more preferable upper limit of the number average molecular weight of the polyester plasticizer is 3000.

The number average molecular weight is a measured value in terms of polystyrene by GPC (gel permeation chromatograph) measurement. The GPC measurement method is performed according to a standard method. A dilute tetrahydrofuran solution of the polyester plasticizer to be measured is prepared and measured using a GPC measuring device “HLC-8220GPC” manufactured by Tosoh Corporation under a flow rate condition of 0.6 ml / min. As the column, “KF606M” and “KF603” manufactured by Showa Denko KK are used.

The polyester plasticizer is preferably an adipic acid polyester plasticizer and having a number average molecular weight of 2000 or more and 3500 or less. Specifically, ADEKA Sizer (registered trademark) (PN-7535, PN-350, P-300) manufactured by ADEKA Corporation can be used.

From the viewpoint of enhancing the flame retardancy of the decorative film of the present invention, the polyvinyl chloride resin layer preferably contains a phthalic acid plasticizer.

The plasticizer content is preferably 0.1 to 35 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. The polyvinyl chloride resin layer in which the content of the plasticizer is less than 0.1 part by weight may not have flexibility capable of following the curved surface shape. On the other hand, when the content of the plasticizer exceeds 35 parts by weight, the amount of the plasticizer that is dissolved or swelled by the solvent increases, and the solvent resistance of the polyvinyl chloride resin layer may decrease. The content of the plasticizer is more preferably 1 to 30 parts by weight, still more preferably 5 to 28 parts by weight.

<Coating layer>
The coating layer of the present invention is colorless and transparent, and is made of a cured product of an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group represented by the following chemical formula (A). Since the coating layer of the present invention is colorless and transparent, for example, even when the coating layer of the present invention is applied to a polyvinyl chloride resin layer such as white, the color tone does not change or hardly changes. Moreover, since the coating layer of this invention is colorless and transparent, even if the number of colors of a polyvinyl chloride-type resin layer increases, it can exhibit performance, without impairing an external appearance design. In the present specification, colorless and transparent means that the light transmittance in the visible light region is 50% or more, preferably 70% or more.

The coating layer preferably has a thickness of 3 μm to 15 μm, and more preferably 5 μm to 15 μm. By setting it as such an aspect, the abrasion resistance and productivity of a decoration film can be improved more.

The coating layer preferably has a gloss value of 90 or more, and more preferably 92 or more. By setting it as such an aspect, glossiness can be provided to the decorating film.

<< UV curable resin composition >>
The ultraviolet curable resin composition of the present invention is a resin composition that contains a polymerization initiator having an acylphosphine oxide group represented by the chemical formula (A) and is cured by irradiation with ultraviolet rays. Moreover, the said ultraviolet curable resin composition may contain additives, such as a modifier and a diluent, as needed in the range which does not impair the effect of this invention.

<<< Polymerization initiator >>>
Since the polymerization initiator having an acylphosphine oxide group represented by the chemical formula (A) has high sensitivity, it is possible to initiate polymerization even when the amount of ultraviolet irradiation is small. That is, the coating layer can be formed while suppressing the integrated light amount. As a result, the UV curable resin composition is sufficiently cured while the surface of the coating layer is made more uniform while solving the processing problem that the polyvinyl chloride resin layer is thermally deteriorated due to UV irradiation. Therefore, the scratch resistance and gloss value of the film can be improved. In addition, since the polymerization can be started with a small amount of ultraviolet irradiation, the productivity can be increased. For example, the speed of the production line can be increased to about twice the normal speed. In the present specification, the polymerization initiator having an acyl phosphine oxide group is also referred to as an acyl phosphine oxide type polymerization initiator or an acyl phosphine oxide type.

From the viewpoint of further improving scratch resistance and productivity, the polymerization initiator having an acylphosphine oxide group is preferably a compound represented by the following chemical formula (A-1).

（上記化学式（Ａ−１）中、Ｒ^１、Ｒ^２２及びＲ^３２は各々独立に炭素数６〜２０の芳香族基を表し、Ｒ^２１及びＲ^３１は各々独立に−ＣＯ−基又は単結合を表す。）

(In the chemical formula (A-1), R ¹ , R ²² and R ³² each independently represents an aromatic group having 6 to 20 carbon atoms, and R ²¹ and R ³¹ each independently represent a —CO— group or a single bond. Represents.)

In said chemical formula (A-1), R < ¹ >, R < ²² > and R < ³² > represent a C6-C20 aromatic group each independently, and it is preferable that it is a C6-C10 aromatic group.

From the viewpoint of further improving scratch resistance and productivity, the polymerization initiator having an acylphosphine oxide group may be at least one of the compounds represented by the following chemical formulas (A-11) and (A-12). More preferred.

<<< Other components contained in UV curable resin composition >>>
The ultraviolet curable resin composition of the present invention preferably contains a resin having a group that is polymerized by ultraviolet rays (ultraviolet curable resin), and preferably contains a urethane (meth) acrylate resin having a group that is polymerized by ultraviolet rays. More preferred. When the ultraviolet curable resin composition of the present invention contains a urethane (meth) acrylate-based resin having a polymerizable reactive group, the scratch resistance of the coating layer can be further improved. In the present specification, “urethane (meth) acrylate” represents “at least one of urethane acrylate and urethane methacrylate”.

<Adhesive layer>
The decorative film of the present invention preferably has a pressure-sensitive adhesive layer, and more preferably has a pressure-sensitive adhesive layer on the surface of the polyvinyl chloride resin layer opposite to the coating layer. Since the decorative film has the pressure-sensitive adhesive layer, the decorative film can be easily attached to the object.

The pressure-sensitive adhesive layer is not particularly limited as long as it has a pressure-sensitive adhesive function (pressure-sensitive adhesiveness), and can contain a pressure-sensitive adhesive usually used in the field of films. Specifically, what contains adhesives, such as an acrylic adhesive, a rubber adhesive, and a silicone adhesive, is mentioned. Among them, an acrylic pressure-sensitive adhesive is preferably used because it is excellent in adhesiveness, workability, heat aging resistance, moisture aging resistance, and weather resistance and is relatively inexpensive. The acrylic pressure-sensitive adhesive may be solvent-based or solvent-free as long as it can exhibit adhesive force at room temperature. Examples of the solvent system include a solvent type adhesive and a non-aqueous emulsion type adhesive. Examples of the solventless system include an emulsion type adhesive and an ultraviolet curable adhesive.

The thickness of the pressure-sensitive adhesive layer is preferably 10 μm or more and 60 μm or less. The more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 20 μm, and the more preferable upper limit is 50 μm.

<Release film, release paper>
The decorative film of the present invention preferably further has a release film or release paper. FIG. 1 is a schematic cross-sectional view showing an example of the decorative film of the present invention having an adhesive layer. As shown in FIG. 1, the decorative film 1a has a coating layer 10, a polyvinyl chloride resin layer 20, an adhesive layer 30, and a release film or release paper 40 laminated in order from the surface. More preferred. By setting it as such an aspect, it becomes possible to affix the decoration film 1a to a target object easily.

As said release film and said release paper, what is normally used in the field | area of a film can be used. Examples of the release film include those obtained by coating the surface of a polyethylene terephthalate (PET) film or the like with a silicone-based, alkyd-based, fluorine-based release agent, or the like. Examples of the release paper include those obtained by coating the surface of fine paper with a silicone-based, alkyd-based, fluorine-based release agent, or the like. The release film or release paper may be subjected to surface treatment only on the surface on the pressure-sensitive adhesive layer side.

<Polyethylene terephthalate resin layer>
The decorative film of the present invention preferably has a polyethylene terephthalate resin layer containing a polyethylene terephthalate resin. FIG. 2 is a schematic cross-sectional view showing an example of the decorative film of the present invention having a polyethylene terephthalate resin layer. As shown in FIG. 2, the decorative film 1 b does not have the pressure-sensitive adhesive layer, the release film, and the release paper, and the surface of the polyvinyl chloride resin layer 20 opposite to the coating layer 10 is It is more preferable to have the polyethylene terephthalate resin layer 50. That is, as for the decorative film 1b, it is more preferable that the coating layer 10, the polyvinyl chloride resin layer 20, and the polyethylene terephthalate resin layer 50 are laminated in order from the surface.

Polyethylene terephthalate resin is less temperature dependent than polyvinyl chloride resin. Therefore, if a decorative film is produced by laminating a polyethylene terephthalate resin layer on a polyvinyl chloride resin layer, the film breakage in the drying furnace can be further suppressed, and the productivity of the decorative film can be further improved. Can do.

The polyethylene terephthalate resin layer preferably has a thickness of 10 μm to 100 μm, and more preferably 20 μm to 80 μm.

[Method for producing decorative film]
The method for producing a decorative film according to the present invention is a method of coating a polyvinyl chloride resin layer with an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group represented by the chemical formula (A). And a coating layer forming step of forming a coating layer by curing the ultraviolet curable resin composition by ultraviolet irradiation.

The polymerization initiator having an acylphosphine oxide group represented by the above chemical formula (A) used in the method for producing a decorative film of the present invention is highly sensitive, and therefore initiates polymerization even when the amount of ultraviolet irradiation is small. It is possible. That is, the coating layer can be formed while suppressing the integrated light amount. As a result, it is possible to solve the processing problem that the polyvinyl chloride resin layer is thermally deteriorated due to ultraviolet irradiation, and a decorative film having improved scratch resistance can be produced. Furthermore, since the polymerization can be started with a small amount of ultraviolet irradiation, the productivity can be increased. For example, the speed of the production line can be increased to about twice the normal speed.

Conventionally, since a polyvinyl chloride resin layer is thermally deteriorated by ultraviolet irradiation, for example, after forming a coating layer on a polyethylene terephthalate resin layer, a film is produced by laminating it with the polyvinyl chloride resin layer. It was. For this reason, the obtained film has disadvantages such as low flexibility and difficulty in elongation, and high cost for film production.

However, in the method for producing a decorative film of the present invention, a coating layer can be formed on the polyvinyl chloride resin layer, so that the flexibility of the decorative film can be improved. Each step will be described in detail below.

<Coating process>
The coating step of the present invention is a step of coating a polyvinyl chloride resin layer with an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group represented by the chemical formula (A). .

Examples of the method for coating the ultraviolet curable resin composition include a gravure coater, a gravure reverse coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a phanten coater, a rod coater, and an air coater. Examples include coating methods using a coater such as a doctor coater, knife coater, blade coater, cast coater, and screen coater, spraying methods using a sprayer such as air spray, airless spray, and rotor dampening, and dipping methods such as dip. It is done. In the coating process of the present invention, it is preferable to use a gravure reverse coater.

<Coating layer formation process>
The coating layer forming step of the present invention is a step of forming the coating layer by curing the ultraviolet curable resin composition by ultraviolet irradiation. The ultraviolet irradiation can be performed using a general ultraviolet irradiation apparatus using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an LED lamp, or the like as a light source. UV accumulated light amount ^is more preferably preferably ^{50mJ / cm 2 ~700mJ / cm 2} , it is ^{100mJ / cm 2 ~500mJ / cm 2} .

<Lamination process>
The method for producing a decorative film of the present invention preferably includes a laminating step of laminating a polyethylene terephthalate resin layer on the polyvinyl chloride resin layer before the coating layer forming step. Thereby, in the manufacturing process of a decoration film, the tolerance | permissible_range of the furnace temperature spreads, and productivity can further be improved.

The polyethylene terephthalate resin layer is more preferably formed on the surface of the polyvinyl chloride resin layer opposite to the side on which the coating layer is formed. The lamination step is not particularly limited, and lamination by lamination is preferable.

When a coating layer is formed on a single-layer polyvinyl chloride resin layer, the polyvinyl chloride resin layer may break due to temperature rise in the drying furnace. A film in a drying furnace in the production process of a decorative film by laminating a polyethylene terephthalate resin layer containing a polyethylene terephthalate resin, which is less temperature dependent than a polyvinyl chloride resin, on the polyvinyl chloride resin layer Can be further suppressed, and the productivity of the decorative film can be further improved. Moreover, the freedom degree of the manufacturing conditions of a decoration film can be raised by laminating | stacking a polyethylene terephthalate resin layer.

<Adhesive layer forming step>
The method for producing a decorative film of the present invention further includes a pressure-sensitive adhesive layer forming step of providing a pressure-sensitive adhesive layer on the surface of the polyvinyl chloride resin layer opposite to the coating layer after the coating layer forming step. It is preferable. Moreover, when the said lamination process is performed, it is preferable to perform the said adhesive layer formation process after the peeling process which peels the polyethylene terephthalate resin laminated | stacked at the said lamination process.

In the pressure-sensitive adhesive layer forming step, for example, a method for preparing a pressure-sensitive adhesive layer-forming composition containing a pressure-sensitive adhesive and applying the pressure-sensitive adhesive forming composition to the polyvinyl chloride resin layer can be used.

EXAMPLES Hereinafter, although an Example and a comparative example are hung up and demonstrated in detail about this invention, this invention is not limited only to these Examples.

[Example 1]
26 parts by weight of a polyester plasticizer is added to 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 1100. After melt-kneading with a Banbury mixer, a support is produced through each roll of the calendar body. A 150 μm polyvinyl chloride resin layer was obtained. A polyethylene terephthalate resin layer having a thickness of 50 μm was laminated on the polyvinyl chloride resin layer to obtain a film in which the polyvinyl chloride resin layer and the polyethylene terephthalate resin layer were laminated.

Next, Daicel Ornex Co., Ltd., EBECRYL8311 was used as the main agent, diluted with ethyl acetate so that the solid content was 30 wt%, and BASF Co., Ltd., IRUGACURE TPO (shown by the above chemical formula (A-11)) was used as the polymerization initiator. The compound (acylphosphine oxide type polymerization initiator) to be added was added at 3 wt% to prepare an ultraviolet curable resin composition. The ultraviolet curable resin composition was coated on the polyvinyl chloride resin layer using a gravure reverse coater so that the film thickness was 5 μm.

Next, the ultraviolet curable resin composition was dried and irradiated with ultraviolet rays so that the accumulated UV light amount was 300 mJ / cm ² to form a coating layer having a thickness of 5 μm, whereby a decorative film of Example 1 was obtained.

[Example 2]
A decorative film of Example 2 was obtained in the same manner as in Example 1 except that 23 parts by weight of diisononyl phthalate (DINP), which is a phthalic acid plasticizer, was used instead of 26 parts by weight of the polyester plasticizer. It was.

[Example 3]
A decorative film of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the coating layer was 3 μm.

[Example 4]
A decorative film of Example 4 was obtained in the same manner as in Example 1 except that the thickness of the coating layer was 15 μm.

[Example 5]
A decorative film of Example 5 was obtained in the same manner as in Example 1 except that the thickness of the polyvinyl chloride resin layer was 80 μm.

[Example 6]
A decorative film of Example 6 was obtained in the same manner as in Example 1 except that the thickness of the polyvinyl chloride resin layer was 200 μm.

[Example 7]
A decorative film of Example 7 was obtained in the same manner as in Example 1 except that the polyethylene terephthalate resin layer was not laminated.

[Example 8]
As in Example 1, except that 3 wt% of IRUGACURE 819 (a compound represented by the above chemical formula (A-12) (acylphosphine oxide type polymerization initiator)) manufactured by BASF Corporation was added as a polymerization initiator. The decorative film of Example 8 was obtained.

[Example 9]
Using EBECRYL8254 manufactured by Daicel Ornex as the main agent, diluted with ethyl acetate so that the solid content is 30 wt%, and then adding 2 wt% of IRUGACURE 819 manufactured by BASF as the polymerization initiator, an ultraviolet curable resin composition was prepared. Prepared. The ultraviolet curable resin composition was coated on the polyvinyl chloride resin layer using a gravure reverse coater so that the film thickness was 5 μm. Except this, it carried out similarly to Example 1, and obtained the decorative film of Example 9.

[Comparative Example 1]
A decorative film of Comparative Example 1 was obtained in the same manner as in Example 1 except that an alkylphenone type polymerization initiator was used instead of the IRUGACURE TPO (acylphosphine oxide type polymerization initiator).

[Evaluation]
About the decorative film produced in the Example and the comparative example, (1) Evaluation of abrasion resistance and (2) Measurement of the gloss value were performed by the following method. Furthermore, based on these results, (3) comprehensive evaluation was performed.

(1) Evaluation of scratch resistance When the decorative film of Example and Comparative Example was rubbed 50 times with a load of 100 g using steel wool of # 0000, the number of scratches was visually evaluated. If the number of scratches is 3 or less (target value), a decorative film having excellent scratch resistance can be provided.

(2) Evaluation of Gloss Value Using a 60 ° gloss meter, the gloss values of the decorative films of Examples and Comparative Examples were measured. If the gloss value is 90 or more (target value), it can be suitably used as a glossy decorative film.

(3) Comprehensive evaluation (1) If the target value is achieved in any of (1) Evaluation of scratch resistance and (2) Gloss value, ○, if there is an item that does not achieve the target value, × .

The evaluation results of Examples and Comparative Examples are shown in Table 1 below.

In any of the examples, the speed of the production line could be increased to about twice the normal speed. In addition, the decorative film produced in the example achieved both the scratch resistance and the gloss value, and the decorative film excellent in the scratch resistance and the gloss value could be produced. Moreover, compared with the decorative film of Example 2 which used the phthalic acid type plasticizer for the polyvinyl chloride-type resin layer, the decorative film of Examples 1 and 3-7 using the non-phthalic acid type polyester plasticizer was used. The one was superior in scratch resistance. The reason why the decorative film using a non-phthalic acid-based polyester plasticizer is more excellent in scratch resistance is considered to be that the plasticizer is not easily transferred.

Moreover, about the Example and the comparative example, the breaking strength of the film before forming a coating layer was evaluated by the following method.

(Evaluation of breaking strength)
About the film before forming a coating layer, the tension test based on JISZ0237 was implemented on conditions with a tensile speed of 300 mm / mim, and the temperature of 60 +/- 2 degreeC, and the load when it fractured was measured. The sample used for the test was collected such that the longitudinal direction of the film (MD (Machine Direction) direction) was the tensile direction. In addition, 60 ± 2 degreeC which is the temperature at the time of performing a test assumes the temperature in the drying furnace in the manufacturing process of a decorative film. If the breaking strength is 20 N / 25 mm or more, the productivity of the decorative film can be further improved. The results are shown in Table 1 above.

In Example 7 in which the polyethylene terephthalate resin layer was not laminated, the breaking strength was lower than 20 N / 25 mm. In other examples, a breaking strength of 20 N / 25 mm or more was obtained, and the productivity of the decorative film was further improved. It was shown that it can.

1a, 1b: Decorative film 10: Coating layer 20: Polyvinyl chloride resin layer 30: Adhesive layer 40: Release film or release paper 50: Polyethylene terephthalate resin layer

Claims (10)

A polyvinyl chloride resin layer;
A colorless and transparent coating layer,
The said coating layer consists of a hardened | cured material of the ultraviolet curable resin composition containing the polymerization initiator which has an acyl phosphine oxide group represented by following Chemical formula (A), The decoration film characterized by the above-mentioned.

The decorative film according to claim 1, wherein the polymerization initiator is a compound represented by the following chemical formula (A-1).

(In the chemical formula (A-1), R ¹ , R ²² and R ³² each independently represents an aromatic group having 6 to 20 carbon atoms, and R ²¹ and R ³¹ each independently represent a —CO— group or a single bond. Represents.) The decorative film according to claim 1 or 2, wherein the polymerization initiator is at least one of compounds represented by the following chemical formulas (A-11) and (A-12).

The decorative film according to any one of claims 1 to 3, wherein the polyvinyl chloride resin layer contains a non-phthalic acid plasticizer. The decorative film according to claim 1, wherein the coating layer has a thickness of 3 μm to 15 μm. The decorative film according to claim 1, wherein the polyvinyl chloride resin layer has a thickness of 80 μm to 200 μm. The decorative film according to claim 1, wherein the coating layer has a gloss value of 90 or more. The decorative film further includes an adhesive layer, a release film or a release paper, and
The said coating layer, the said polyvinyl chloride-type resin layer, the said adhesive layer, and the said release film or release paper are laminated | stacked in order from the surface. Decoration film. A coating step of coating a polyvinyl chloride resin layer with an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group represented by the following chemical formula (A);
A coating layer forming step of forming the coating layer by curing the ultraviolet curable resin composition by ultraviolet irradiation;
A method for producing a decorative film, comprising:

The method for producing a decorative film according to claim 9, further comprising a laminating step of laminating a polyethylene terephthalate resin layer on the polyvinyl chloride resin layer before the coating layer forming step.

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