JP2021035723A - Decorative film, and method for producing three-dimensional molded article having decorative film - Google Patents

Abstract

To provide a decorative film having exceptional stain resistance with respect to a sunscreen, and a method for producing a three-dimensional molded article having the decorative film.SOLUTION: This decorative film has a base film, and a fluorine-containing layer that includes a fluorine-containing polymer, where the chlorine atom content of the fluorine-containing layer is 1 to 35 mass% and, in the fluorine-containing layer, a ratio of the chlorine atom content to the fluorine atom content is 0.05 to 30.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative film and a method for manufacturing a three-dimensional molded product with a decorative film.

The surface of a three-dimensional molded product used in the field of interior / exterior products for automobiles may be decorated with a decorative film for the purpose of imparting design and protecting the surface. Patent Document 1 discloses a decorative film having a fluorine-containing layer containing polyvinylidene fluoride.

Japanese Unexamined Patent Publication No. 2014-184726

If the sunscreen adheres to the three-dimensional molded product, it may cause contamination and deterioration of the three-dimensional molded product.
The present inventors have found that a decorative film having a fluorine-containing layer containing polyvinylidene fluoride described in Patent Document 1 is inferior in stain resistance to sunscreens.

In view of the above problems, an object of the present invention is to provide a decorative film having excellent stain resistance to a sunscreen and a method for producing a three-dimensional molded product with the decorative film.

As a result of diligent studies on the above problems, the present inventors have found that the chlorine atom content of the fluorine-containing layer containing the fluorine-containing polymer is within a predetermined range, and the ratio of the chlorine atom content to the fluorine atom content is We have found that a desired effect can be obtained within a predetermined range, and have reached the present invention.
That is, the present inventors have found that the above problems can be solved by the following configuration.

[1] A decorative film having at least a base film layer and a fluorine-containing layer containing a fluorine-containing polymer.
The chlorine atom content of the fluorine-containing layer is 1 to 35% by mass.
A decorative film characterized in that the ratio of the chlorine atom content to the fluorine atom content in the fluorine-containing layer is 0.05 to 30.
[2] Difference between the chlorine atom content existing in the region from the surface of the fluorine-containing layer to a depth of 2 μm and the chlorine atom content existing in the region from the surface of the fluorine-containing layer to a depth of 2 to 4 μm in the fluorine-containing layer. The decorative film according to [1], wherein the absolute value of is 5.0% by mass or less.
[3] The decorative film according to [1] or [2], wherein the fluorine atom content in the fluorine-containing layer is 3 to 50% by mass.
[4] The fluorine-containing layer is a layer containing one or more of the fluorine-containing polymers, and the glass transition temperature of the one or more of the fluorine-containing polymers is 20 to 150. The decorative film according to any one of [1] to [3], which is at ° C.
[5] The decorative film according to any one of [1] to [4], which further has an adhesive layer.
[6] The decorative film is laminated in the order of the adhesive layer, the fluorine-containing layer, and the base film layer, and is laminated so that the fluorine-containing layer and the base film layer are in contact with each other. The decorative film according to [5].
[7] The decorative film according to [5], wherein the decorative film is laminated in the order of the adhesive layer, the base film layer, and the fluorine-containing layer.
[8] The decorative film according to any one of [1] to [7], which is used for decorating a three-dimensional molded product used for an automobile exterior part or an automobile interior part.
[9] With the decorative film according to any one of [1] to [8] and the surface to be decorated of the three-dimensional molded product, the decorative film is pressure-bonded under reduced pressure to have the fluorine-containing layer on the outermost surface. A method for manufacturing a three-dimensional molded product with a decorative film, which obtains a three-dimensional molded product.

According to the present invention, it is possible to provide a decorative film having excellent stain resistance to a sunscreen agent and a method for producing a three-dimensional molded product with the decorative film.

It is a schematic side view which shows an example of the laminated structure of the decorative film of this invention. It is a schematic side view which shows an example of the laminated structure of the decorative film of this invention.

The meanings of the terms in the present invention are as follows.
The numerical range represented by "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
"(Meta) acrylate" is a general term for acrylate and methacrylate, and "(meth) acrylic" is a general term for "acrylic" and "methacrylic".
The "unit" is a general term for an atomic group derived from one molecule of the monomer, which is directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group. is there. The "unit based on a monomer" is also simply referred to as a "unit" below. The content (mol%) of each unit with respect to all the units contained in the polymer is determined by analyzing the polymer by a nuclear magnetic resonance spectrum (NMR) method.
The "acid value" and "hydroxyl value" are values measured according to the method of JIS K 0070-3 (1992), respectively.
The "glass transition temperature" is the midpoint glass transition temperature of the polymer as measured by the differential scanning calorimetry (DSC) method. The "glass transition temperature" is also referred to as "Tg".
The "softening temperature" is a value measured according to the method of JIS K 7196 (1991).
The "number average molecular weight" and the "weight average molecular weight" are values measured by gel permeation chromatography using polystyrene as a standard substance. The "number average molecular weight" is also referred to as "Mn", and the "weight average molecular weight" is also referred to as "Mw".

The "chlorine atom content of the fluorine-containing layer" and the "fluorine atom content of the fluorine-containing layer" mean the content (mass%) of each atom with respect to all the atoms constituting the fluorine-containing layer. The chlorine atom content and the fluorine atom content of the fluorine-containing layer can be obtained by measuring under the following conditions by an automatic sample combustion device-ion chromatography method (AQF-IC method).
<Analysis conditions>
-Automatic sample combustion device: Automatic sample combustion device AQF-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
Combustion conditions: Solid sample mode Sample amount: 2 to 20 mg
-Ion chromatograph device: Thermo Fisher SCIENTIFIC column: IonpacAG11HC + IonpacAS11HC
Eluent: KOH 10mN (0-9min), 10-16mN (9-11min), 16mN (11-15min), 16-61mN (15-20min), 60mN (20-25min)
Flow velocity: 1.0 mL / min Suppressor: ASRS
Detector: Conductivity detector Injection amount: 5 μL

"Chlorine atom content existing in the region from the surface of the fluorine-containing layer to a depth of 2 μm" and "Chlorine atom content existing in a region having a depth of 2 to 4 μm from the surface of the fluorine-containing layer" are applied to each region of the fluorine-containing layer. It means the content (% by mass) of chlorine atoms with respect to all existing atoms, and is obtained by measuring the cross section of the fluorine-containing layer under the following conditions with a scanning electron microscope equipped with an energy dispersive X-ray analyzer.
<Analysis conditions>
SEM: Hitachi High-Tech, SU6600
EDX: manufactured by HORIBA, Ltd., Emax X-max80
Acceleration voltage: 10kV
Coat: Platinum (10 kV, surface coat in 40 seconds)
SEM observation conditions: reflected electron image (COMPO image)
Observation magnification: 20000 times EDX mapping measurement time: 10 minutes

The "fluorine atom content" and "chlorine atom content" in the fluorine-containing polymer mean the ratio (mass%) of each atom to all the atoms constituting the fluorine-containing polymer. The fluorine atom content and the chlorine atom content in the fluorine-containing polymer can be determined by analyzing the fluorine-containing polymer by a nuclear magnetic resonance spectrum method.
The mass of the "solid content" of the coating material and the fluorine-containing polymer composition is the mass obtained by removing the solvent from the coating material and the fluorine-containing polymer composition when the coating material and the fluorine-containing polymer composition contain a solvent.

The film thickness of each layer is measured using an eddy current type film thickness meter (trade name "EDY-5000", manufactured by Sanko Denshi Co., Ltd.).

The water vapor transmittance of this decorative film is a value measured according to the method of JIS Z0208.

The decorative film of the present invention (hereinafter, also referred to as "the present decorative film") is a decorative film having at least a base film layer and a fluorine-containing layer containing a fluorine-containing polymer, and is a fluorine-containing layer. The chlorine atom content of the film is 1 to 35% by mass, and the ratio of the chlorine atom content to the fluorine atom content in the fluorine-containing layer is 0.05 to 30.
This decorative film has excellent stain resistance to sunscreens. In the following, the term "staining resistance" refers to the stain resistance to sunscreens such as Copatone (registered trademark). In addition, stain resistance to sunscreens may be referred to as "sun oil resistance".

The fluorine-containing layer in the present decorative film has a chlorine atom content and a ratio of the chlorine atom content to the fluorine atom content within a predetermined range.
When the ratio of the chlorine atom content to the fluorine atom content is within a predetermined range, the arrangement state of the fluorine-containing polymer in the decorative film and the arrangement state between the polymers are caused by the interaction between the fluorine atom and the chlorine atom. Is preferable, and it is considered that chlorine atoms are likely to be uniformly distributed and present in the fluorine-containing layer. Furthermore, it is considered that the effect of suppressing the adhesion or invasion of the sunscreen agent is improved by the action of chlorine atoms, and if the chlorine atoms are uniformly distributed in the fluorine-containing layer, the adhesion of the sunscreen agent to the fluorine-containing layer or Since intrusion can be suppressed, it is considered that the stain resistance of this decorative film is excellent.

First, the configuration of the decorative film of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic side view showing a laminated structure of a decorative film 10 according to an embodiment of the present invention. The decorative film 10 has an adhesive layer 12, a fluorine-containing layer 14, and a base film layer 16, and each layer is laminated in this order.
Further, in the example of FIG. 1, the fluorine-containing layer 14 and the base film 16 are arranged so as to be in contact with each other. However, when the release layer described later is provided between the fluorine-containing layer 14 and the base film 16, the fluorine-containing layer 14 and the base film 16 do not have to be in contact with each other.
The adhesive layer 12 of the decorative film 10 and the surface to be decorated of the three-dimensional molded product (described later) are pressure-bonded under reduced pressure, and then the base film 16 is peeled off from the decorative film 10 to form the fluorine-containing layer 14. A three-dimensional molded product with a decorative film is obtained in which the adhesive layers 12 and the three-dimensional molded product are laminated in this order. As described above, the fluorine-containing layer 14 is located on the outermost surface of the three-dimensional molded product with the decorative film.
Since the fluorine-containing layer 14 contains a fluorine-containing polymer described later, it is excellent in releasability from the base film 14.

FIG. 2 is a schematic side view showing a laminated structure of the decorative film 100 according to another embodiment of the present invention. The decorative film 100 has an adhesive layer 120, a base film layer 160, and a fluorine-containing layer 140, and each layer is laminated in this order.
By crimping the adhesive layer 120 of the decorative film 100 and the decorated surface of the three-dimensional molded product (described later) under reduced pressure, the fluorine-containing layer 140, the base film layer 160, the adhesive layer 120, and the three-dimensional molded product A three-dimensional molded product with a decorative film laminated in this order can be obtained. As described above, the fluorine-containing layer 140 is located on the outermost surface of the three-dimensional molded product with the decorative film.

Although not shown in FIGS. 1 and 2, the decorative film may have a design layer in order to improve the designability of the decorative film. The design layer is preferably arranged between the adhesive layer and the fluorine-containing layer.
Specifically, when the decorative film 10 of FIG. 1 has a design layer, an aspect in which the adhesive layer 12, the design layer, the fluorine-containing layer 14, and the base film layer 16 are laminated in this order can be mentioned.
When the decorative film 100 of FIG. 2 has a design layer, the adhesive layer 120, the design layer, the base film layer 160, and the fluorine-containing layer 140 are laminated in this order, and the adhesive layer 120 and the base film layer. An embodiment in which 160, a design layer, and a fluorine-containing layer 140 are laminated in this order can be mentioned.
The adhesive layer or the base film layer may also serve as the design layer, and in this case, the design layer may not be provided.
Further, in the examples of FIGS. 1 and 2, the case where the decorative film 10 has the adhesive layer 12 has been described as an example, but the present invention is not limited to this, and the decorative film can be attached to the three-dimensional molded product. If so, the decorative film does not have to have an adhesive layer.
That is, the present decorative film may have at least a base film layer and a fluorine-containing layer.

The decorative film preferably has an adhesive layer from the viewpoint of adhesion to the three-dimensional molded product.
The adhesive layer is a layer for adhering the decorative film and the three-dimensional molded product, and preferably contains an adhesive resin. The adhesive layer can be formed by using, for example, an adhesive coating film forming agent containing an adhesive resin, and may be referred to as an adhesive coating film.
The adhesive resin is one selected from the group consisting of urethane resin, (meth) acrylic resin, olefin resin, vinyl chloride-vinyl acetate resin, epoxy resin and butyral resin because of its excellent adhesiveness to three-dimensional molded products. It is preferable to contain the above resin.

The softening temperature of the adhesive resin is preferably 20 to 100 ° C., particularly preferably 25 to 90 ° C., from the viewpoint of blocking resistance and moldability of the decorative film.
The Mw of the adhesive resin is preferably 5000 to 150,000, particularly preferably 6000 to 130,000 from the viewpoint of film forming property and adhesiveness.

The adhesive coating film forming agent (adhesive layer) may contain a curing agent. The curing agent is preferably a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, which will be described later. When the adhesive coating film forming agent (adhesive layer) contains a curing agent, the adhesive resin preferably has a hydroxyl group.
The adhesive layer may also have the function of the design layer described later. In this case, if the adhesive layer contains a colorant or the like, an adhesive layer having a function as a design layer can be obtained.

The adhesive coating film forming agent (adhesive layer) may contain components other than the above. Specific examples of components other than the above include organic ultraviolet absorbers, which will be described later, organic light stabilizers, which will be described later, curing catalysts, antioxidants, surface conditioners, leveling agents, anti-sagging agents, and thickeners, which will be described later. Examples include defoaming agents, conductive fillers and organic solvents.
The film thickness of the adhesive layer is preferably 0.001 to 0.1 mm, more preferably 0.004 to 0.08 mm, and particularly preferably 0.01 to 0.06 mm from the viewpoint of film forming property and adhesiveness.

The base film layer functions as a support film for supporting each layer when the decorative film is produced.
Specific examples of the materials constituting the base film layer include vinyl chloride resin, polyester resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), (meth) acrylic resin, olefin resin, and fluorine-containing polymer of the present invention. Examples thereof include a fluororesin containing a fluoropolymer (a fluoropolymer containing no chlorine atom, such as polyvinylidene fluoride). Among these, the material constituting the base film layer preferably contains one or more selected from the group consisting of vinyl chloride resin, polyester resin, ABS resin, meta (acrylic) resin, and the above-mentioned fluororesin.
The film thickness of the base film layer is preferably 0.01 to 0.5 mm, particularly preferably 0.02 to 0.3 mm.

The base film layer may have an uneven pattern on at least one side. The uneven pattern can be formed by a processing method such as embossing, hairline processing, or chemical etching processing.
If the base film has an uneven pattern, the decorative film after the base film is peeled off also has an uneven pattern, so that the design property due to the uneven pattern can be imparted to the three-dimensional molded product with the decorative film. ..

Since the fluorine-containing layer contains a fluorine-containing polymer, it is excellent in antifouling property, durable weather resistance, chemical resistance and the like. Therefore, a three-dimensional molded product with a decorative film having a fluorine-containing layer has the same effect.
The fluorine-containing polymer contained in the fluorine-containing layer may or may not be cured. In any case, the fluorine-containing layer has already formed a certain coating film (layer) before being used for manufacturing a three-dimensional molded product with a decorative film. Therefore, when the present decorative film and the three-dimensional molded product are attached, volatilization of components contained in layers other than the fluorine-containing layer can be suppressed.
The fluorine-containing layer can be formed, for example, by using a fluorine-containing polymer composition containing a fluorine-containing polymer described later.
In the present specification, when the fluorine-containing layer is present on the outermost surface of the decorative film, the fluorine-containing layer may be referred to as a top layer. Further, the fluorine-containing polymer composition used for forming the top layer may be referred to as a "top coating film forming agent".

The fluorine-containing layer contains a predetermined amount of chlorine atoms as described later. Examples of the chlorine atom contained in the fluorine-containing layer include a chlorine atom contained in the fluorine-containing polymer and a chlorine atom contained in a component other than the fluorine-containing polymer (for example, a polymer containing a chlorine atom).
Specific examples of such a fluorine-containing layer containing a chlorine atom include a fluorine-containing layer containing a chlorine atom contained in a fluorine-containing polymer, a fluorine-containing layer containing a chlorine atom contained in a component other than the fluorine-containing polymer, and a fluorine-containing layer. , A fluorine-containing layer containing both a chlorine atom contained in a fluorine-containing polymer and a chlorine atom contained in a component other than the fluorine-containing polymer.
Among these, the fluorine-containing layer containing chlorine atoms contained in the fluorine-containing polymer is easy to be present in the fluorine-containing layer with uniform distribution of chlorine atoms, and the stain resistance of the decorative film is more excellent. Is preferable.

The fluorine-containing polymer is selected from the group consisting of a unit based on a fluoroolefin (hereinafter, also referred to as "unit F"), a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, and a (meth) acrylic acid ester. A unit based on a monomer of seed or more (hereinafter, also referred to as "monomer 1") (hereinafter, also referred to as "unit 1") and a monomer having a crosslinkable group (hereinafter, "monomer"). It is preferable to include a unit based on (also referred to as "unit 2") (hereinafter, also referred to as "unit 2").

A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. In the fluoroolefin, one or more hydrogen atoms which are not substituted with fluorine atoms may be substituted with chlorine atoms.
Specific examples of fluoroolefins include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CHF, CH ₂ = CF ₂ , CF ₂ = CFCF ₃ , CF ₂ = CHCF ₃ , CF ₃ CH = CHF, CF ₃ CF = CH _{2 is mentioned, and CF 2} = CF ₂ , CF ₂ = CFCl, CF ₃ CH = CHF or CF ₃ CF = CH ₂ is preferable from the viewpoint of copolymerizability, and CF 3 CF = CH 2 is more preferable. CF ₂ = CFCl is particularly preferable. Fluoroolefins may be used alone or in combination of two or more.
The content of the unit F is preferably 20 to 70 mol%, more preferably 40 to 60 mol%, based on the weather resistance of the present decorative film, based on all the units contained in the fluorine-containing polymer.

Unit 1 is a unit based on one or more monomers (monomer 1) selected from the group consisting of vinyl ether, vinyl ester, allyl ether, allyl ester, and (meth) acrylic acid ester. Unit 1 preferably does not contain a fluorine atom.

Unit 1 is a unit based on a monomer represented by the formula ^X 1 -Y ¹ are preferred.
X ¹ is CH ₂ = CHC (O) O-, CH ₂ = C (CH ₃ ) C (O) O-, CH ₂ = CHOC (O)-, CH ₂ = CHCH ₂ OC (O)-, CH ₂ = CHO- or CH ₂ = CHCH _{2 O-, and CH 2} = CHOC (O)-, CH ₂ = CHCH ₂ OC (O)-, CH ₂ = from the viewpoint of excellent weather resistance of this decorative film. CHO − or CH ₂ = CHCH ₂ O− is preferable.

Y ¹ is a monovalent hydrocarbon group having 1 to 24 carbon atoms. The monovalent hydrocarbon group may be linear or branched. Further, the monovalent hydrocarbon group may have a ring structure or may contain a ring structure. Further, the monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.
The monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and is an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Alternatively, an aralkyl group having 7 to 12 carbon atoms is particularly preferable.
Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a hexyl group, a nonyl group, a decyl group and a dodecyl group.
Specific examples of the cycloalkyl group include a cyclohexyl group.
Specific examples of the aralkyl group include a benzyl group.
Specific examples of the aryl group include a phenyl group and a naphthyl group.
The hydrogen atom of the cycloalkyl group, aryl group or aralkyl group may be substituted with an alkyl group. In this case, the carbon number of the alkyl group as the substituent is not included in the carbon number of the cycloalkyl group or the aryl group.

Two or more types of monomer 1 may be used in combination.
Specific examples of the monomer 1 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, pivalic acid vinyl ester, and neononanoic acid vinyl ester (manufactured by HEXION, trade name "Beova 9"). , Neodecanoic acid vinyl ester (manufactured by HEXION, trade name "Beova 10"), benzoic acid vinyl ester, tert-butyl benzoic acid vinyl ester, tert-butyl (meth) acrylate, benzyl (meth) acrylate.
The content of the unit 1 is preferably 5 to 60 mol%, particularly preferably 10 to 50 mol%, based on all the units contained in the fluorine-containing polymer.

Specific examples of the crosslinkable group contained in the monomer 2 include a hydroxyl group, a carboxy group, an amino group, and an alkoxysilyl group, and a hydroxyl group or a carboxy group is preferable from the viewpoint of further improving the scratch resistance of the fluorine-containing layer. .. Further, the unit 2 preferably does not contain a fluorine atom.

The monomer 2 is ^{a monomer represented by the formula X 21-} Y ²¹ (hereinafter, also referred to as "monomer 21") and a monomer represented by the ^{formula X 22-} Y ^{22 (hereinafter, "monomer 21").} Also referred to as "monomer 22") or allyl alcohol is preferred.
The symbols in the formula have the following meanings.
X ²¹ is CH ₂ = CH −, CH (CH ₃ ) = CH − or CH ₂ = C (CH ₃ ) −, and CH ₂ = CH − or CH (CH ₃ ) = CH − is preferable.
Y ²¹ is a carboxy group or a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and having a carboxy group, and a carboxy group or a carboxyalkyl group having 1 to 10 carbon atoms is preferable.
X ²² is CH ₂ = CHO−, CH ₂ = CHCH ₂ O−, CH ₂ = CHCOO− or CH ₂ = C (CH ₃ ) COO−.
Y ²² is a monovalent saturated hydrocarbon group having 2 to 12 carbon atoms and having a hydroxyl group. The monovalent saturated hydrocarbon group may be linear or branched. Further, the monovalent saturated hydrocarbon group may have a ring structure or may contain a ring structure.
The monovalent saturated hydrocarbon group is preferably an alkyl group having 2 to 6 carbon atoms or an alkyl group containing a cycloalkylene group having 6 to 8 carbon atoms.

Specific examples of the monomer 21 include CH ₂ = CHCOOH, CH (CH ₃ ) = CHCOOH, CH ₂ = C (CH ₃ ) COOH, and a compound represented by _{the formula CH 2} = CH (CH ₂ ) _{n2 COOH (} However, n2 indicates an integer of 1 to 10).
Specific examples of the monomer 22 include CH ₂ = CHO-CH _2- cycloC ₆ H _10- CH ₂ OH, CH ₂ = CHCH ₂ O-CH _2- cycloC ₆ H _10- CH ₂ OH, CH ₂ = CHOCH. ₂ CH ₂ OH, CH ₂ = CHCH ₂ OCH ₂ CH ₂ OH, CH ₂ = CHOCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ = CHCOOCH ₂ CH ₂ OH, CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ OH can be mentioned. In addition, "-cycloC ₆ H _10- " represents a cyclohexylene group, and the binding site of " _{-cycloC 6} H _{10-" is usually 1,4-.}
The monomer 2 may be used alone or in combination of two or more.
Further, the monomer 2 may have two or more kinds of crosslinkable groups.
When the fluorine-containing polymer contains unit 2, the crosslinkable group contained in the fluorine-containing polymer contained in the fluorine-containing layer of the present decorative film is in a state in which the crosslinkable group remains without being crosslinked. It may be in a state of being crosslinked with a curing agent described later or a polymer other than the fluorine-containing polymer in the present invention.

When the fluorine-containing polymer has a cross-linked structure with a curing agent, the cross-linking group of unit 2 serves as a cross-linking point, and cross-linking between the fluorine-containing polymers is performed via the curing agent. Therefore, the hardness of the fluorine-containing layer is improved, and the physical properties of the coating film such as weather resistance, water resistance, chemical resistance, heat resistance, and extensibility are improved.
The content of unit 2 is preferably 0.5 to 35 mol%, more preferably 3 to 25 mol%, particularly preferably 5 to 25 mol%, and 5 to 20 with respect to all the units contained in the fluorine-containing polymer. Mol% is most preferred.

The fluorine atom content of the fluorine-containing polymer is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass from the viewpoint of more excellent weather resistance of the present decorative film.
The chlorine atom content of the fluorine-containing polymer is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and particularly preferably 10 to 40% by mass from the viewpoint of more excellent stain resistance of the decorative film. ..
The fluorine-containing polymer contains units F, unit 1 and unit 2 in this order of 20 to 70 mol%, 5 to 60 mol% and 0.5 to 35 mol% with respect to all the units of the fluorine-containing polymer. It is preferable to include it.
The Tg of the fluorine-containing polymer is preferably 20 to 150 ° C., more preferably 30 to 100 ° C., further preferably 50 to 80 ° C., and particularly preferably 40 to 60 ° C. from the viewpoint of excellent stain resistance of the decorative film. preferable. When the Tg of the fluorinated polymer is room temperature or higher (20 ° C or higher), the motility of the fluorinated polymer in the fluorinated layer is suppressed under a normal environment in which a sunscreen is used, and the fluorinated polymer contains fluorine. It is considered that the state in which chlorine atoms are uniformly distributed in the layer is easily maintained. When the present decorative film contains a plurality of fluorine-containing polymers, it is preferable that the Tg of each of the fluorine-containing polymers is within the above range.
The Mn of the fluorine-containing polymer is preferably 3,000 to 30,000, more preferably 5,000 to 25,000, and particularly preferably 7,000 to 20,000, from the viewpoint of followability of the fluorine-containing layer.
When the fluorine-containing polymer is a fluorine-containing polymer containing a carboxy group, the acid value of the fluorine-containing polymer is 1 to 150 mgKOH / g from the viewpoint of impact resistance, flexibility and chemical resistance of the present decorative film. Is preferable, 3 to 100 mgKOH / g is more preferable, and 5 to 50 mgKOH / g is particularly preferable.
When the fluorine-containing polymer is a fluorine-containing polymer containing a hydroxyl group, the hydroxyl value of the fluorine-containing polymer is 1 to 150 mgKOH / g from the viewpoint of impact resistance, flexibility and chemical resistance of the present decorative film. Preferably, 3 to 100 mgKOH / g is more preferable, and 10 to 60 mgKOH / g is particularly preferable.
The fluorine-containing polymer may have either an acid value or a hydroxyl value, or may have both. When the fluorine-containing polymer has both an acid value and a hydroxyl value, the total of the acid value and the hydroxyl value is preferably 1 to 150 mgKOH / g.
When the total of the acid value and the hydroxyl value is within the above range, the Tg of the fluorine-containing polymer can be suitably adjusted, and the physical characteristics (impact resistance, flexibility, chemical resistance, etc.) of this decorative film are good. It becomes.
The content of the fluorine-containing polymer in the fluorine-containing layer is preferably 30 to 100% by mass, more preferably 35 to 90% by mass, based on the total mass of the fluorine-containing layer from the viewpoint of weather resistance of the present decorative film. It is preferable, and 40 to 80% by mass is particularly preferable.

The fluorine-containing layer may contain a polymer that does not contain a fluorine atom and contains a chlorine atom (hereinafter, also referred to as “chlorine-containing polymer”).
The chlorine-containing polymer preferably contains a unit based on vinyl chloride. The chlorine-containing polymer may be a homopolymer of a unit based on vinyl chloride, or a copolymer containing a unit based on vinyl chloride and a unit based on a monomer other than vinyl chloride. May be good.
Specific examples of monomers other than vinyl chloride include α-olefins (eg, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1). -Hexene, 1-hexene, 1-octene, 1-decene), vinyl esters (vinyl acetate, etc.) can be mentioned.
The Mn of the chlorine-containing polymer is preferably 2000 to 80,000, and particularly preferably 3000 to 70000.
The Tg of the chlorine-containing polymer is preferably 25 to 150 ° C, particularly preferably 30 to 100 ° C.
When the fluorine-containing layer contains a chlorine-containing polymer, the content of the chlorine-containing polymer in the fluorine-containing layer may be appropriately determined so that the chlorine content of the fluorine-containing layer is within a predetermined range (described later).

The fluorine-containing layer preferably contains a crosslinked structure between the fluorine-containing polymers via a curing agent from the viewpoint of excellent hardness of the decorative film. In this case, the fluorine-containing polymer has a crosslinkable group, and the crosslinkable group forms the above-mentioned crosslinked structure.
A curing agent is a compound having two or more groups in one molecule that can react with a crosslinkable group. When the curing agent reacts with the crosslinkable group contained in the fluorine-containing polymer, the fluorine-containing polymer is crosslinked and the fluorine-containing layer is cured. The curing agent usually has 2 to 30 groups capable of reacting with the crosslinkable group.
When the fluorine-containing polymer has a hydroxyl group, the curing agent is preferably a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.
When the fluorine-containing polymer has a carboxy group, the curing agent is preferably a compound having two or more epoxy groups, carbodiimide groups, oxazoline groups or β-hydroxyalkylamide groups in one molecule.
When the fluorine-containing polymer has both a hydroxyl group and a carboxy group, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule and an epoxy group, a carbodiimide group, an oxazoline group or a β-hydroxyalkylamide group are used. It is preferable to use in combination with a compound having two or more in one molecule.

The compound having two or more isocyanate groups in one molecule is preferably a polyisocyanate monomer or a polyisocyanate derivative.
The polyisocyanate monomer is preferably an alicyclic polyisocyanate, an aliphatic polyisocyanate or an aromatic polyisocyanate. The polyisocyanate derivative is preferably a multimer or a modified form (biuret form, isocyanurate form or adduct form) of the polyisocyanate monomer.

Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, and aliphatic diisocyanates such as lysine diisocyanate and lysine triisocyanate. Examples thereof include isocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and bis (2-isocyanatoethyl) 2-isocyanatoglutarate.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate. Can be mentioned.
Specific examples of the aromatic polyisocyanate include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, and xylylene diisocyanate.

From the viewpoint of extensibility of the decorative film, the curing agent is preferably a modified polyisocyanate monomer, more preferably an adduct body of a polyisocyanate monomer, and particularly preferably an adduct body of hexamethylene diisocyanate.

The compound having two or more blocked isocyanate groups in one molecule is preferably a compound in which two or more isocyanate groups of the above-mentioned polyisocyanate monomer or polyisocyanate derivative are blocked by a blocking agent.
The blocking agent is a compound having active hydrogen, and specific examples thereof include alcohol, phenol, active methylene, amine, imine, acid amide, lactam, oxime, pyrazole, imidazole, imidazoline, pyrimidine, and guanidine.

Specific examples of compounds having two or more epoxy groups in one molecule include bisphenol type epoxy compounds (A type, F type, S type, etc.), diphenyl ether type epoxy compounds, hydroquinone type epoxy compounds, naphthalene type epoxy compounds, and biphenyl type. Epoxy compounds, fluorene-type epoxy compounds, hydrogenated bisphenol A-type epoxy compounds, bisphenol A-containing polyol-type epoxy compounds, polypropylene glycol-type epoxy compounds, glycidyl ester-type epoxy compounds, glycidylamine-type epoxy compounds, glioxal-type epoxy compounds, alicyclic Examples thereof include type epoxy compounds, alicyclic polyfunctional epoxy compounds, and heterocyclic epoxy compounds (triglycidyl isocyanate, etc.).

Specific examples of compounds having two or more carbodiimide groups in one molecule include alicyclic carbodiimides, aliphatic carbodiimides, and aromatic carbodiimides, and multimers and modified products thereof.

Specific examples of the compound having two or more oxazoline groups in one molecule include addition-polymerizable oxazoline having a 2-oxazoline group and a polymer of the addition-polymerizable oxazoline.

Specific examples of compounds having two or more β-hydroxyalkylamide groups in one molecule include N, N, N', N'-tetrakis- (2-hydroxyethyl) -adipamide (PrimidXL-552, manufactured by EMS). , N, N, N', N'-tetrakis- (2-hydroxypropyl) -adipamide (Primid QM 1260 Primid XL-552, manufactured by EMS).

The fluorine-containing layer may contain a curing catalyst. The curing catalyst is a compound that promotes a curing reaction when a curing agent is used, and can be selected from known curing catalysts according to the type of curing agent.

The fluorine-containing layer preferably contains one or more selected from the group consisting of an organic ultraviolet absorber and an organic light stabilizer.
That is, the fluorine-containing polymer composition may contain both an organic ultraviolet absorber and an organic light stabilizer, or may contain only one of them.

The organic ultraviolet absorber is a compound that protects the decorative film from ultraviolet rays.
As the organic ultraviolet absorber, salicylic acid ester compounds, benzotriazole compounds, benzophenone compounds, and cyanoacrylate compounds are preferable.
Specific examples of the organic ultraviolet absorber include "Tinuvin 326" (molecular weight: 315.8, melting point: 139 ° C.), "Tinuvin 328-2" (molecular weight: 351, melting point: 82 ° C.), and "Tinuvin" manufactured by BASF. "400" (molecular weight: 647), "Tinuvin 405" (molecular weight: 583.8, melting point: 74-77 ° C.), "Tinuvin 460" (molecular weight: 629.8, melting point: 93-102 ° C.), "Tinuvin 900" (Molecular weight: 447.6, melting point: 137 to 141 ° C.), "Tinuvin 928" (molecular weight: 441.6, melting point: 109 to 113 ° C.), "Sanduvor VSU powerer" (molecular weight: 312.0, melting point) manufactured by Clariant. : 123-127 ° C.), Clarant's "Hastavin PR-25 Gran" (molecular weight: 250.0, melting point: 55-59 ° C.).
Two or more kinds of organic ultraviolet absorbers may be used in combination.
When the fluorine-containing layer contains an organic ultraviolet absorber, the content of the organic ultraviolet absorber is 0.001 to 1 with respect to the total mass of the fluorine-containing layer in terms of the total light transmittance of the fluorine-containing layer. The mass% is preferable, and 0.005 to 0.1 mass% is particularly preferable.

The organic light stabilizer is a compound that improves the light resistance of the present decorative film.
As the organic light stabilizer, a hindered amine compound is preferable. Specific examples of the hindered amine compound include "Tinuvin 111FDL" (molecular weight: 2000 to 4000, melting point: 63 ° C.), "Tinuvin 144" (molecular weight: 685, melting point: 146 to 150 ° C.), and "Tinuvin 152" (molecular weight: 2000 to 4000 ° C.) Molecular weight: 756.6, melting point: 83-90 ° C., "Tinuvin 292" (molecular weight: 508.8, melting point: 20 ° C.), Clarant's "Sanduvor 3051 powerer" (molecular weight: 364.0, melting point: 225 ° C.) ), Clarant's "Sanduvor 3070 power" (molecular weight: 1,500, melting point: 148 ° C.), Clariant's "VP Sanduvor PR-31" (molecular weight: 529, melting point: 120-125 ° C.).
The organic light stabilizer may be used alone or in combination of two or more.
When the fluorine-containing layer contains an organic light stabilizer, the content of the organic light stabilizer is preferably 0.01 to 15% by mass, preferably 0.1 to 3% by mass, based on the total mass of the fluorine-containing layer. Is particularly preferable.

The fluorine-containing layer may contain a fluorine-containing polymer other than the fluorine-containing polymer in the present invention, and may contain a fluorine-containing polymer and a resin other than the chlorine-containing polymer.
Specific examples of the fluorine-containing polymer other than the fluorine-containing polymer in the present invention include polyvinylidene fluoride. Specific examples of the fluoropolymer and the resin other than the chlorine-containing polymer include alkyd resin, aminoalkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, vinyl acetate resin, acrylic resin, phenol resin, and modification. Examples thereof include polyester resin, acrylic silicone resin, and silicone resin.

The fluorine-containing layer contains components other than the above, for example, various media (water, organic solvent, etc.), fillers (inorganic fillers such as silica, organic fillers such as resin beads, etc.), inorganic ultraviolet absorbers, and matte, if necessary. Agents, leveling agents, surface conditioners, degassing agents, fillers, heat stabilizers, thickeners, dispersants, surfactants, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, low pollution It may contain a chemical treatment agent and a plasticizer.

The chlorine atom content of the fluorine-containing layer is 1 to 35% by mass, preferably 5 to 25% by mass, and particularly preferably 7 to 20% by mass. When the chlorine atom content of the fluorine-containing layer is 1% by mass or more, the stain resistance of the decorative film is excellent. Further, when the chlorine atom content of the fluorine-containing layer is 35% by mass or less, the weather resistance of the present decorative film is excellent. Further, the chlorine atom content of the fluorine-containing layer is preferably 20% by mass or less from the viewpoint of excellent gasoline resistance of the decorative film.
In the fluorine-containing layer, the chlorine atom content existing in the region from the surface of the fluorine-containing layer to a depth of 2 μm and the chlorine atom content existing in the region from the surface of the fluorine-containing layer to a depth of 2 to 4 μm are the present decorative film. From the viewpoint of more excellent stain resistance, 1 to 35% by mass is preferable, 5 to 25% by mass is more preferable, and 7 to 20% by mass is particularly preferable.
Further, the difference between the chlorine atom content existing in the region from the surface of the fluorine-containing layer to the depth of 2 μm in the fluorine-containing layer and the chlorine atom content existing in the region having a depth of 2 to 4 μm from the surface of the fluorine-containing layer. The absolute value is preferably 5.0% by mass or less, more preferably 3.5% by mass or less, and particularly preferably 1.0% by mass or less. As described above, if the chlorine atoms are more uniformly distributed and present in the fluorine-containing layer, the stain resistance of the present decorative film is more excellent. Further, the absolute value of the above difference is preferably 3.5% by mass or less because the decorative film is excellent in gasoline resistance.

The fluorine atom content in the fluorine-containing layer is preferably 3 to 50% by mass, more preferably 7 to 40% by mass, and particularly preferably 10 to 30% by mass from the viewpoint of weather resistance and stain resistance of the decorative film. , 10 to 20% by mass is more preferable.
The ratio of the chlorine atom content to the fluorine atom content in the fluorine-containing layer is 0.05 to 30, preferably 0.1 to 20, more preferably 0.2 to 10, and particularly 0.3 to 5. It is preferable, and 0.5 to 3.5 is more preferable. When the ratio of the chlorine atom content to the fluorine atom content in the fluorine-containing layer is within the above range, the interaction between the fluorine atom and the chlorine atom is good, and the chlorine atom in the fluorine-containing layer is more uniformly distributed. It is thought that.

The Tg of the fluorine-containing layer is preferably 0 to 150 ° C., more preferably 10 to 100 ° C., particularly preferably 20 to 80 ° C., in that the stain resistance of the decorative film is more excellent.
The film thickness of the fluorine-containing layer is preferably 5 to 200 μm, particularly preferably 10 to 100 μm. This decorative film is excellent in moldability regardless of whether it is a thin film or a thick film.

The fluorine-containing layer is preferably formed by using a fluorine-containing polymer composition containing a fluorine-containing polymer. The fluorine-containing polymer contained in the fluorine-containing polymer composition is the same as the fluorine-containing polymer in the fluorine-containing layer described above, and the preferred embodiment is also the same, and thus the description thereof will be omitted.
The content of the fluorinated polymer in the fluorinated polymer composition is 5 to 90% by mass with respect to the total mass of the solid content contained in the fluorinated polymer composition from the viewpoint of weather resistance of the present decorative film. Is preferable, and 10 to 80% by mass is particularly preferable.

Further, the fluorine-containing polymer composition is one or more selected from the group consisting of a chlorine-containing polymer, a curing agent, a curing catalyst, an organic ultraviolet absorber and an organic light stabilizer, and the fluorine-containing polymer in the present invention. A fluorinated polymer other than the above, a resin other than the fluorinated polymer, and a component that may be contained in the above-mentioned fluorine-containing layer may be contained, and the details of each are the same as described above, and thus the description thereof will be omitted.
When the fluorine-containing polymer composition contains a curing agent, the content of the curing agent is preferably 10 to 200 parts by mass, preferably 50 to 150 parts by mass, based on 100 parts by mass of the fluorine-containing polymer in the fluorine-containing polymer composition. Parts by mass are particularly preferred.
When the fluorine-containing polymer composition contains an organic ultraviolet absorber, the content of the organic ultraviolet absorber is the total solid content contained in the fluorine-containing polymer composition from the viewpoint of the total light transmittance of the fluorine-containing layer. With respect to the mass, 0.001 to 1% by mass is preferable, and 0.005 to 0.1% by mass is particularly preferable.
When the fluorine-containing polymer composition contains an organic light stabilizer, the content of the organic light stabilizer is 0.01 to 15% by mass with respect to the mass of the total solid content contained in the fluorine-containing polymer composition. Is preferable, and 0.1 to 3% by mass is particularly preferable.

The decorative film may have a design layer. The design layer is a layer for imparting design to a three-dimensional molded product.
Specific examples of the design layer include a layer formed by using a design coating film forming agent, a layer formed by a printing method, and a layer formed by a metal vapor deposition method.
The layer formed by using the design coating film forming agent is formed by applying the design coating film forming agent, and is also referred to as a design coating film. The components contained in the design coating film forming agent include binder resin (urethane resin, (meth) acrylic resin, etc.), colorant (dye, organic pigment, inorganic pigment, bright pigment using metal, mica, etc.), solvent. (Water, organic solvent, etc.) and the like.
The layer formed by the printing method is formed by using an ink (including, for example, a binder resin, a colorant, and a solvent) suitable for each printing method such as inkjet printing, screen printing, offset printing, and flexographic printing.
The layer formed by the metal vapor deposition method is formed by using a metal such as aluminum, indium, or tin.
The design layer may contain components other than the above, if necessary, and specific examples thereof include the components listed in the adhesive coating film forming agent and the components listed in the fluorine-containing polymer composition.
The film thickness of the design layer is not particularly limited, and may be appropriately set according to the intended use.
The design layer can also serve as the above-mentioned adhesive layer, base film layer, and fluorine-containing layer.

The decorative film may have a layer other than the above, and examples thereof include a release layer and a protective layer.
The release layer is a layer that can be provided when the base film 16 is finally peeled off, as in the decorative film 10 of FIG. In the aspect of FIG. 1, the release layer is preferably provided between the base film layer 16 and the fluorine-containing layer 14 so as to be in contact with the base film 16. The release layer can be formed by using, for example, a silicone-based release agent.
The protective layer is a layer that can be provided for the purpose of protecting the design layer, and is preferably provided so as to be in contact with the design layer. The protective layer can be formed by using a resin such as (meth) acrylic resin, urethane resin, or ABS resin.

For each layer other than the base film constituting the present decorative film, for example, each coating film forming agent in which the components constituting each layer are dissolved in a solvent (water, organic solvent, etc.) is prepared, and each coating film forming agent is prepared. Can be formed by coating on a base film and drying.
Specific examples of the coating method for forming each layer include a method using a spray, an applicator, a die coater, a bar coater, a roll coater, a comma coater, a roller brush, a brush, and a spatula.
After applying each coating film forming agent, it may be heated and dried in order to remove the solvent in the coating film forming agent.
Here, when the fluorine-containing polymer composition used for forming the fluorine-containing layer is a so-called powder coating material, the fluorine-containing layer can also be formed by electrostatic coating or the like.
Further, as described above, the design layer can also be formed by a method other than coating (printing method, thin-film deposition method).
Further, the fluorine-containing layer and the adhesive layer may be formed in the form of a film in advance, and these may be laminated and laminated on any layer.

Water vapor permeability of the decorative film is preferably less than 100g ^/ m 2 ^/ day, and particularly preferably ^60g / m 2 / day. As a result, the moisture absorption of the decorative film can be suppressed, so that the stain resistance of the decorative film is more excellent.
The water vapor permeability of the decorative film can be controlled, for example, by the ratio of the chlorine atom content to the fluorine atom content in the fluorine-containing layer and the Tg of the fluorine-containing polymer contained in the fluorine-containing layer.

The present decorative film is preferably stretched and used in order to impart designability to the decorated body (for example, a three-dimensional molded product described later) or to protect the surface of the decorated body. The stretching direction and stretching method of the decorative film can be appropriately selected depending on the shape of the three-dimensional molded product, the manufacturing conditions at the time of molding, and the like. The extension direction may be any direction, and the extension method may be any method. That is, the extension of the decorative film may be carried out by pulling the decorative film in a predetermined one direction or all directions, or the decorative film may be appropriately heated and expanded.

This decorative film is suitably used for decorating a three-dimensional molded product used for an automobile exterior part or an automobile interior part. Specific examples of the three-dimensional molded products used for automobile exterior parts and automobile interior parts will be described later.

The three-dimensional molded article with a decorative film of the present invention (hereinafter, also referred to as "the present molded body") is obtained by pressing the present decorative film and the decorated surface of the three-dimensional molded article under reduced pressure.
The crimping method under reduced pressure in the method for producing this molded product is also called a vacuum forming method (overlay molding method), and can be carried out using, for example, a double-sided vacuum forming apparatus.
Under reduced pressure means a state in which the pressure is lower than the standard atmospheric pressure. Specifically, the pressure under reduced pressure is preferably 70 kPa or less.
In the method for producing the present molded product, the decorative film may be cured after the decorative film and the surface to be decorated of the three-dimensional molded product are pressure-bonded under reduced pressure. Curing of the decorative film can be carried out, for example, by heating. The heating temperature is preferably 50 to 150 ° C.

When the decorative film 10 as shown in FIG. 1 is used, the present molded product can be obtained by peeling off the base film after pressure bonding under reduced pressure. In this case, the curing of the decorative film may be performed at any timing before and after the base film is peeled off.

Further, the three-dimensional molded product with a decorative film of the present invention may be appropriately obtained by a molding method other than the vacuum forming method. Specific examples of such a molding method include in-mold molding, in-mold transfer molding, in-mold pasting synthetic type, overlay transfer molding, overlay pasting synthetic type, hydraulic transfer and the like. Further, the decorative film may be pressure-bonded to the three-dimensional molded product before molding and then processed to obtain the three-dimensional molded product with the decorative film.

Specific examples of the materials constituting the three-dimensional molded product include polypropylene, ABS resin, and polycarbonate.
Specific examples of the three-dimensional molded product include automobile exterior parts such as door mirrors, front under spoilers, rear under spoilers, side underskirts, bumpers, and side garnishes, and automobile interior parts such as center consoles, instrument panels, and door switch panels. ..

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. The blending amount of each component in the table described later indicates a mass standard. Further, Examples 1 to 4 are Examples, and Examples 5 to 8 are Comparative Examples.

<Abbreviation of ingredients used>
Tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hydroxybutyl vinyl ether (HBVE), cyclohexyl vinyl ether (CHVE), neodecanoic acid vinyl ester (V10), neononanoic acid vinyl ester (V9), benzoate vinyl ester (VBn) ), Vinyl acetate (VA), polyvinylidene fluoride (PVDF), vinyl chloride (VC)
<Polymer used>
Fluorine-containing polymer 1 solution: A polymer containing 50 mol%, 11 mol%, and 39 mol% of units based on CTFE, HBVE, and CHVE in this order (hydroxyl value 51 mgKOH / g, Tg55 ° C., fluorine. A butyl acetate solution (polymer concentration 50% by mass) with an atomic content of 24.7% by mass and a chlorine atom content of 15.3% by mass)
Fluorine-containing polymer 2 solution: A polymer containing 44 mol%, 9 mol%, and 47 mol% of a unit based on CTFE, a unit based on HBVE, and a unit based on V10 in this order (hydroxyl value 33 mgKOH / g, Tg17 ° C., fluorine. A butyl acetate solution (polymer concentration 50% by mass) with an atomic content of 16.2% by mass and a chlorine atom content of 10.1% by mass)
Fluorine-containing polymer 3 solution: TFE-based unit, HBVE-based unit, V9-based unit, VBn-based unit, VA-based unit, in this order, 45 mol%, 14 mol%, 31 mol%, 6 mol%. Butyl acetate solution of a polymer containing 4 mol% (hydroxyl value 9 mgKOH / g, Tg 35 ° C., fluorine atom content 26.1% by mass, chlorine atom content 0% by mass) (polymer concentration 50% by mass)
Fluorine-containing polymer 4 solution: PVDF (hydroxyl value 0 mgKOH / g, Tg-40 ° C., fluorine atom content 53.2% by mass, chlorine atom content 0% by mass) N-methyl-2-pyrrolidone solution (polymer) Concentration 50% by mass)
Non-fluorine polymer 1 solution: A polymer containing 86 mol% and 14 mol% of VC-based units and VA-based units in this order (hydroxyl value 0 mgKOH / g, Tg78 ° C., fluorine atom content 0% by mass, chlorine atom. Fluorine acetate solution (content 48.8% by mass) (polymer concentration 50% by mass)

<Additives>
Curing agent: E405-70B (Compound having two or more isocyanate groups in one molecule (adduct), manufactured by Asahi Kasei Corporation)
Curing catalyst: ADEKA STAB BT-11 (manufactured by ADEKA)
Plasticizer 1: Polyoxypropylene glyceryl ether (polyester triol, molecular weight 3000)
Plasticizer 2: Polysizer W-230-H (manufactured by DIC, polyester, molecular weight 1000)
Organic UV absorber: TINUVIN384-2 (manufactured by BASF)
Surface conditioner: KF69 (dimethyl silicone oil, manufactured by Shinetsu Silicone Co., Ltd.)
Defoamer: Disparon OX-66 (manufactured by Kusumoto Kasei Co., Ltd.)

<Manufacturing of decorative films and molded products>
[Examples 1 to 8]
A top coating film forming agent obtained by mixing each component shown in Table 1 is applied onto a base film (polyurethane resin) using an applicator, and dried at 80 ° C. for 5 minutes to obtain a top coating film (average). A top layer having a film thickness of 20 μm) was formed.
Next, a design coating film forming agent (TU240 FDSS, manufactured by Toyo Ink Co., Ltd.) is applied to the surface of the base film on which the top layer is not formed, and dried at 80 ° C. for 5 minutes to provide a design coating film (film). A design layer having a thickness of 10 μm) was formed.
Next, the adhesive coating film forming agent (acrylic adhesive) was applied onto the design coating film and dried at 80 ° C. for 5 minutes to form an adhesive layer composed of the adhesive coating film (thickness 20 μm).
By the above method, a decorative film 1 in which the top layer, the base film, the design layer, and the adhesive layer are laminated in this order was obtained.
Decorative films 2 to 8 and molded products 2 to 8 were obtained in the same manner except that the top coating film forming agent 1 was changed to the top coating film forming agents 2 to 8, and were subjected to the evaluation described later. The evaluation results are shown in Table 1 below.

<Physical characteristics of the top layer>
Tg, chlorine atom content of fluorine-containing polymer, difference between chlorine atom content existing in the region from the top layer surface to a depth of 2 μm and chlorine atom content existing in the region from the top layer surface to a depth of 2 to 4 μm Absolute value (indicated as "Chlorine atom content difference" in the table), fluorine atom content, ratio of chlorine atom content to fluorine atom content in the top layer (in the table, "ratio (Cl / F)) ”) Was measured according to the method described above. The measurement results are shown in Table 1.

<Evaluation method>
[Sun oil resistance of decorative film]
After 1 mL of a sunscreen (Copatone Water Babies Lotion SPF50) was added dropwise to the top layer of the decorative film obtained in the above production, the mixture was allowed to stand at 80 ° C. for 8 hours. After that, the sunscreen was wiped off with gauze, the decorative film was washed with water, and changes in the top layer were visually observed. The evaluation criteria are as follows. The evaluation results are shown in Table 1.
◯: No change is observed in the top layer.
Δ: A slight change is observed in the top layer.
×: A fatal change is observed in the top layer.

[Gasoline resistance of decorative film]
After 1 mL of gasoline (unleaded gasoline described in JIS K2202 2) was added dropwise to the top layer of the decorative film obtained in the above production, the mixture was allowed to stand at 80 ° C. for 8 hours. After that, changes in the top layer were visually observed. The evaluation criteria are as follows. The evaluation results are shown in Table 1.
◯: No change is observed in the top layer.
Δ: A slight change is observed in the top layer.
×: A fatal change is observed in the top layer.

[Water vapor permeability of decorative film]
The water vapor permeability of the decorative film was evaluated according to JIS Z0208. The evaluation criteria are as follows. The evaluation results are shown in Table 1.
◯: The water vapor transmittance is 60 g / m ² / day or less.
△: water vapor permeability is less than ^60g / m 2 / day ultra 100g ^/ m 2 ^/ day.
X: The water vapor permeability is 100 g / m ² / day or more.

As shown in Table 1, when the chlorine atom content of the top layer is 1 to 35% by mass and the ratio of the chlorine atom content to the fluorine atom content is 0.05 to 30, the decorative film is used. It was confirmed that it has excellent sun oil resistance.

10,100 Decorative film 12,120 Adhesive layer 14,140 Fluorine-containing layer 16,160 Base film layer

Claims (9)

A decorative film having at least a base film layer and a fluorine-containing layer containing a fluorine-containing polymer.
The chlorine atom content of the fluorine-containing layer is 1 to 35% by mass.
A decorative film characterized in that the ratio of the chlorine atom content to the fluorine atom content in the fluorine-containing layer is 0.05 to 30. Absolute difference between the chlorine atom content in the region from the surface of the fluorine-containing layer to a depth of 2 μm and the chlorine atom content in the region from the surface of the fluorine-containing layer to a depth of 2 to 4 μm in the fluorine-containing layer. The decorative film according to claim 1, wherein the value is 5.0% by mass or less. The decorative film according to claim 1 or 2, wherein the fluorine atom content in the fluorine-containing layer is 3 to 50% by mass. The fluorinated layer is a layer containing one or more of the fluorinated polymers, and the glass transition temperature of the one or more fluorinated polymers is 20 to 150 ° C. , The decorative film according to any one of claims 1 to 3. The decorative film according to any one of claims 1 to 4, further comprising an adhesive layer. 5. The decorative film is laminated in the order of the adhesive layer, the fluorine-containing layer, and the base film layer, and is laminated so that the fluorine-containing layer and the base film layer are in contact with each other. Decorative film described in. The decorative film according to claim 5, wherein the decorative film is laminated in the order of the adhesive layer, the base film layer, and the fluorine-containing layer. The decorative film according to any one of claims 1 to 7, which is used for decorating a three-dimensional molded product used for an automobile exterior part or an automobile interior part. The decorative film according to any one of claims 1 to 8 and the surface to be decorated of the three-dimensional molded product are pressure-bonded under reduced pressure, and the three-dimensional molding with the decorative film having the fluorine-containing layer on the outermost surface. A method for manufacturing a three-dimensional molded product with a decorative film to obtain a product.