JP2014231221A - Decorative film for transfer - Google Patents

Abstract

[Purpose] The present invention is an in-mold injection molding simultaneous transfer decoration method, which can be adjusted to an optimum peel strength without forming a release layer on a base film, which was necessary in the past. It aims at providing a film at low cost. It is another object of the present invention to provide a decorative film for transfer that can impart excellent scratch resistance and hardness to the surface of a molded product when the hard coat layer is completely cured by active energy rays. A decorative decorative film for transfer having a hard coat layer, wherein the hard coat layer is formed by contacting a base film with a resin composition semi-cured by active energy rays. The composition contains an active energy ray-curable resin (A) and a photopolymerization initiator (B), and the active energy ray-curable resin (A) has a weight average molecular weight of 10,000 to 100,000. The decorative film for transfer is a polyfunctional (meth) acrylate having a molecular weight of 200 to 400 per (meth) acryloyl group. [Selection figure] None

Description

The present invention relates to a decorative film for transfer. Specifically, the present invention relates to a decorative film for transfer used in an in-mold injection molding simultaneous transfer decorative method for imparting functionality and design to the surface of a plastic molded product.

As a manufacturing method to give decorations such as patterns and textures and scratch resistance (hard coat properties) to the surface of plastic products, adhesive layers, pattern layers, and hard coat layers are laminated on plastic films such as PET (polyethylene terephthalate). An in-mold injection molding method is used in which the decorated film is inserted into a mold and attached to a molded product at the same time as injection molding.

Such an in-mold injection molding method is classified into an injection molding simultaneous transfer decoration method and an injection molding simultaneous laminate decoration method depending on the difference in the configuration of a decorative film to be attached to a resin molded product.

In the injection molding simultaneous transfer decoration method, a release layer is formed on one side of a base film, and a transfer layer (a layer in which a hard coat layer, a pattern layer, an adhesive layer, etc. are stacked in this order) is stacked on the release layer. Insert the decorative film for transfer into the mold, place the base film side in close contact with the inner surface of the mold, and inject the molten thermoplastic resin into the mold from the transfer layer side after closing the mold After filling, when the mold is opened and the molded product is taken out, the release layer and the hard coat layer are peeled off, whereby the transfer layer is transferred to the outermost surface to obtain a molded product. In such an injection molding simultaneous transfer decoration method, peeling is likely to occur at the interface between the hard coat layer and the release layer during transfer, and peeling is likely to occur at the interface between the release layer and the hard coat layer. There was a problem that the release layer and the hard coat layer were peeled off when the decorative film was conveyed.

For this, it is a transfer decorative film in which a release layer, a protective layer, a colored layer and an adhesive layer are laminated in this order on a substrate, and the protective layer is a polymerizable (meth) acrylate. A transfer decorative film comprising a cured product of an ionizing radiation curable resin composition containing an oligomer and having a peel strength between the release layer and the protective layer after transfer of 0.1 to 1.0 N / 25 mm is proposed. (For example, refer to Patent Document 1). In addition, in the hard coat layer transfer foil in which a release layer, a hard coat layer, and an adhesive layer are provided on one surface of the base material and the base material, the release layer is a melamine resin, and the hard coat layer is A hard coat layer transfer foil containing a cured product of ionizing radiation curable resin and polyethylene wax has also been proposed (see, for example, Patent Document 2).

However, the decorative film for transfer having these release layers has to be laminated with a release layer, leading to cost deterioration and an increase in the number of steps required for production, which causes a decrease in production efficiency. .

In addition, the hard coat layer transfer foil described in Patent Document 2 has a low adhesiveness between the hard coat layer and the molded product. When the hard coat layer and the pattern ink layer are simultaneously decorated on the molded product, There was a problem that the adhesion between the coat layer and the pattern ink layer deteriorated.

In this way, in the injection molding simultaneous transfer decorating method, the hard coat and the transfer layer (hard coat layer, picture layer and adhesive layer) that give decoration etc. and the base film are easily peeled off, There has been a demand for the development of a decorative film for transfer which can be easily and inexpensively injection-molded without peeling off the layer from the pattern layer.

JP 2011-8421 A JP 2008-6708 A

In the in-mold injection molding simultaneous transfer decoration method, the present invention can easily form the release layer on the base film at the interface between the base film and the hard coat layer without forming a release layer on the base film. An object of the present invention is to provide a decorative film for transfer which can be peeled off, has an excellent coating film elongation, and has a hard coat layer after complete curing having excellent scratch resistance and hardness.

As a result of intensive research, the inventors set the peel strength at the interface between the base film and the hard coat layer within an appropriate range by controlling the resin composition and curability of the hard coat layer, even without a release layer. The knowledge that can be. That is, the present invention is a decorative film for transfer having a hard coat layer, the hard coat layer is formed by contacting a base film with a resin composition semi-cured by active energy rays, The resin composition contains an active energy ray curable resin (A) (hereinafter also referred to as “component (A)”) and a photopolymerization initiator (B) (hereinafter also referred to as “component (B)”). The energy ray curable resin (A) is a polyfunctional (meth) acrylate having a weight average molecular weight of 10,000 to 100,000 and a molecular weight of 200 to 400 per (meth) acryloyl group. Is a decorative film for transfer. (Hereinafter referred to as the present invention 1).

The present invention 2 is obtained by reacting an α, β-unsaturated carboxylic acid with a radical polymer of a monomer component in which the active energy ray-curable resin (A) contains at least an epoxy group-containing (meth) acrylate monomer. It is a decorative film for transfer which is a reaction product.

Invention 3 is a decorative film for transfer according to Invention 1 or 2, wherein the peel strength between the base film and the hard coat layer is 30 to 500 mN / 24 mm.

According to the present invention, in the in-mold injection molding simultaneous transfer decorating method, the base film and the transfer layer are hardly peeled off during transportation without forming a release layer on the base film, which has been necessary in the past. The transfer layer can be peeled off from the base film without unevenness at the time of transfer molding, and a decorative film for transfer that can be adjusted to the optimum peel strength can be obtained at low cost. Excellent scratch resistance and hardness can be imparted to the molding surface.

The decorative film for transfer in the present invention is used in an in-mold injection molding simultaneous transfer decorative method used for imparting functionality and design to the surface of a plastic molded product. In the decorative film for transfer of the present invention, a hard coat layer is formed in contact with the base film, and a release layer which has been conventionally required between the base film and the hard coat layer is unnecessary.

The said hard-coat layer makes the resin composition (hard-coat agent) containing (A) component and (B) component a semi-hardened material by an active energy ray.

The component (A) is a polyfunctional (meth) acrylate having a molecular weight of 200 to 400 per (meth) acryloyl group and a weight average molecular weight of 10,000 to 100,000. When the molecular weight per (meth) acryloyl group is less than 200, actual synthesis is difficult, and when it exceeds 400, the hard coat property is lowered and the surface of the molded product is easily damaged. Preferably, it is 200-300. When the weight average molecular weight is less than 10,000, the peel strength becomes high and it becomes difficult to peel off the base film and the hard coat layer. Further, the surface tack is large and the blocking resistance is lowered, and when it exceeds 100,000, The resin becomes too viscous and difficult to handle. Preferably, it is 100,000-90,000. A weight average molecular weight here is the value measured from the weight average molecular weight obtained by the polystyrene conversion value by the gel permeation chromatography (GPC) method. The molecular weight per (meth) acryloyl group is a value calculated from {weight average molecular weight of component (A) / sum of acryloyl groups}.

The component (A) is preferably a reaction product obtained by reacting a radical polymer of a monomer component containing at least an epoxy group-containing (meth) acrylate monomer with an α, β-unsaturated carboxylic acid. Thereby, a hard coat layer having high hardness and excellent scratch resistance can be obtained.

The epoxy group-containing (meth) acrylate monomer contained in the monomer component is a compound having at least one epoxy group and one unsaturated double bond in the molecule. Specifically, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene monooxide (ie, 1,2-epoxy-4-vinylcyclohexane) Etc. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of availability and procurement cost.

The monomer component in the component (A) can contain a copolymerizable monomer in addition to the epoxy group-containing (meth) acrylate monomer.

As the above copolymerizable monomer, (meth) acrylic acid ester, styrene, vinyl acetate, (meth) acrylamide, acrylonitrile, which has an unsaturated double bond at one end and does not contain an epoxy group or a carboxyl group Macromonomer etc. are mentioned. Among these, one or more kinds can be contained as a monomer component.

Specific examples of the macromonomer include, for example, Toagosei Co., Ltd. Macromonomer AA-6, AB-6, AS-6, AY-707S, Chisso Corporation Silaplane FM-0711, FM-0721, Daicel Chemical Industrial Co., Ltd. Plaxel FA10L, NOF Corporation Bremer PME-4000, PSE-1300, etc. are mentioned.

As the α, β-unsaturated carboxylic acid, various known ones can be used without particular limitation. Specific examples include α, β-unsaturated monocarboxylic acids such as (meth) acrylic acid and α, β-unsaturated dicarboxylic acids such as (meth) acrylic acid dimer. Of these, (meth) acrylic acid is preferred from the viewpoint of hard coat layer hard coat properties obtained by completely curing the resin composition.

The component (B) is not particularly limited as long as it can start polymerization by generating radicals with active energy rays, and a known component can be used. Specific examples of the component (B) include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[( -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide, 4-methylbenzophenone, 1- [4- (4-benzoylphenylsulfanyl) phanyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 1,2-octane Dione, 1- [4- (phenylthio) phenyl, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) etc. are mentioned. (B) component can be used individually or in combination of 2 or more types.

The blending amount of the component (A) and the component (B) in the resin composition is such that the component (B) is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin solid content of the component (A). Is preferred. By using this blending amount, it is easy to form a semi-cured hard coat layer by controlling curability, and it is difficult to cause poor curing even when the hard coat layer is completely cured by irradiation with active energy rays after transfer.

The resin composition may contain an inorganic filler for the purpose of improving wear resistance and blocking resistance. As the inorganic filler, known ones such as silica fine particles and metal oxide fine particles can be used without limitation. Examples of the metal oxide fine particles include titanium oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, and indium oxide. These can be used individually by 1 type or in combination of 2 or more types. Of these, fine particles of silica, titanium oxide, aluminum oxide, zirconium oxide and zinc oxide are preferred because they are commercially available, readily available, and inexpensive. Moreover, the silica particle which surface-treated especially is preferable at the point which can provide the decoration film for transcription | transfer which has the outstanding blocking resistance. When mix | blending an inorganic filler with a resin composition, it is preferable that an inorganic filler is about 1-30 weight part with respect to 100 weight part of resin solid content of (A) component. By setting it as this range, it can be set as the decoration film for transcription | transfer which has the outstanding blocking resistance.

The surface-treated silica is composed of normal hexane necessary for the total light transmittance of a solution obtained by adding normal hexane to 10 g of a mixed solution of silica fine particles: methyl isobutyl ketone: methyl ethyl ketone = 1: 3: 6 to be 60 to 70%. Hydrophobic surface-treated silica fine particles having a dropping amount of 10 g or more are preferred. By setting it as this range, the decorative film for transfer excellent in blocking resistance can be obtained.

It is preferable to use an inorganic filler whose average particle size is controlled to about 1 to 200 nm (by laser diffraction / scattering method). When the average particle size is less than 1 nm, the storage stability is poor, and when the average particle size exceeds 200 nm, the cured film is likely to be whitened, and optical properties such as haze and transmission efficiency may be impaired. More preferably, the average particle size is 1 to 100 nm.

The decorative film for transfer of the present invention has a blocking resistance when the monomer component which is the raw material of the component (A) contains the macromonomer and / or when the resin composition contains hydrophobic surface-treated silica particles. It is preferable in that it is particularly excellent.

The resin composition is a leveling agent or antifoaming agent for improving coatability, a commercially available ultraviolet absorber for improving light resistance, a glycerin fatty acid ester for the purpose of adjusting peel strength from a substrate film, Polyglycerin fatty acid ester, sorbitan fatty acid ester, fatty acid amide and the like can also be blended.

The base film is not particularly limited, and for example, polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, or the like is used. it can.

In the present invention, the hard coat layer formed in contact with the substrate film is obtained by semi-curing the resin composition with active energy rays.

The semi-curing is a state in which a part of the (meth) acryloyl group in the active energy ray-curable resin undergoes a crosslinking reaction and an unreacted (meth) acryloyl group remains. This was measured by a reflection ATR measuring method by an infrared spectrometry, and the peak area P1620 in the vicinity of a wavelength of 1620 cm ^-1, the value of the ratio of the peak area P1720 in the vicinity of a wavelength of 1720cm ^-1 (P1620 / P1720), the following formula The degree of cure represented by (1) means 0.7 or more and 0.95 or less.
Curing degree = (P1620 after UV irradiation / P1720 after UV irradiation) / (P1620 before UV irradiation / P1720 before UV irradiation)

The semi-cured resin composition has low tackiness and blocking resistance that prevents the resin component from adhering to the finger when touching the surface of the semi-cured coating film, and excellent coating film elongation.

As a method of laminating a semi-cured film (hard coat layer) on the base film, (1) it is applied by a known method and dried to satisfy the above hardness, or (2) it is applied and dried. This is performed by irradiating and curing energy rays so as to satisfy the above hardness later. Examples of the method for applying the hard coating agent include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. The coating amount is not particularly limited, but is usually within a range where the weight after drying is 0.1 to 20 g / m ² , preferably 0.5 to 10 g / m ² .

The transfer decorative film is usually a transfer layer such as a pattern ink layer, an anchor layer, an adhesive layer, a low reflection layer, an antistatic layer, an ultraviolet absorption layer, a near infrared blocking layer, an electromagnetic wave absorption layer, etc. You may laminate | stack in any order on the hard-coat layer which is a semi-hardened material.

In the pattern ink layer, pigments and dyes of appropriate colors are blended in polyvinyl resin, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, cellulose resin, alkyd resin, and the like. The color ink is laminated using a printing method such as gravure coating, reverse gravure coating, offset printing, screen printing, and the like. This pattern ink layer may be monochromatic or multicolored. Moreover, metal vapor deposition can also be performed entirely or partially.

The anchor layer uses a thermoplastic resin such as a two-component curable urethane resin, a melamine, an epoxy thermosetting resin, a vinyl chloride resin, or a polyacrylic resin in order to improve the adhesion between the transfer layers. And can be laminated by a known printing method.

The adhesive layer is necessary for bringing the transfer layer into close contact with the surface of the molded product. The entire surface or only the portion to be transferred is laminated. As the adhesive layer, a polyacrylic resin, a polystyrene resin, a polyamide resin, an indene resin, or the like having a suitable affinity can be used in combination with one or more of them depending on the material of the molded product.

The above-mentioned decorative film for transfer can be used in the in-mold injection molding simultaneous transfer decorative method. For example, after the decorative film for transfer is continuously conveyed by a conveyance roll or the like into a mold composed of a fixed mold and a movable mold, the base film side is in contact with the fixed mold surface, and an appropriate position adjustment is made. The movable mold moves and clamps. The thermoplastic resin previously melted by heat is injected and filled into the mold from the transfer layer side of the decorative film for transfer at high temperature and pressure, and after rapid cooling, the mold is opened and the transfer layer is transferred to the outermost surface. Take out the molded product.

The peel strength between the substrate film and the hard coat layer is preferably 30 to 500 mN / 24 mm. By setting the peel strength within this range, the base film and the hard coat layer can be handled without being peeled when transported into the mold, and the peeling unevenness occurs when the base film is peeled from the hard coat layer at the same time as the transfer. It is possible to achieve excellent transferability without the occurrence of the above. More preferably, it is 40-300mN / 24mm, More preferably, it is 50-200mN / 24mm.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and% are based on weight unless otherwise specified.

<Preparation of active energy-ray curable resin (polyfunctional (meth) acrylate)>
<Synthesis Example 1>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet, 48.6 parts of butyl acetate, 32.6 parts of glycidyl methacrylate (hereinafter, GMA), azobisisobutyronitrile (hereinafter, (AIBN) 1.6 parts were charged and stirred, and the mixture was heated to 100 ° C. by nitrogen stream and reacted for 10 hours. After completion of the reaction, the reaction solution is cooled to 60 ° C., charged with 16.6 parts of acrylic acid, 0.1 part of triphenylphosphine and 0.5 part of methoquinone, and replaced the nitrogen inlet with an air bubbling device to bring air into the reaction solution. The mixture was stirred while bubbling, and the temperature was raised to 110 ° C. and reacted for 9 hours to obtain a resin 1 having a resin solid content of 50% (Table 1). In addition, the weight average molecular weight (polystyrene conversion value by GPC) was 12,000, and the molecular weight per acrylic group was calculated to be 214. The weight average molecular weight was measured by connecting gel permeation chromatography (trade name “HLC-8220”, manufactured by Tosoh Corp., column: manufactured by Tosoh Corp., product name “TSKgel superHZ2000” in series). Indicates.

<Synthesis Example 2>
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet was charged with 49.2 parts of butyl acetate, 33.0 parts of GMA, and 0.3 part of AIBN, and stirred at 85 ° C. with a nitrogen stream. The reaction was allowed to proceed for 10 hours. After completion of the reaction, the reaction solution is cooled to 60 ° C., charged with 16.8 parts of acrylic acid, 0.1 part of triphenylphosphine and 0.5 part of methoquinone, and replaced the nitrogen inlet with an air bubbling device to bring air into the reaction solution. The mixture was stirred while bubbling and heated up to 110 ° C. for 9 hours to obtain a resin 2 having a resin solid content of 50% (Table 1). In addition, the weight average molecular weight (polystyrene conversion value by GPC) was 60,000, and the calculated molecular weight per acrylic group was 214.

<Synthesis Example 3>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet, 48.8 parts of butyl acetate, 28.0 parts of GMA, 3.5 parts of ethyl acrylate (EA), methyl methacrylate (MMA) 3.5 parts and 1.4 parts of AIBN were charged and stirred, and the temperature was raised to 90 ° C. by nitrogen flow, followed by reaction for 10 hours. After completion of the reaction, the reaction solution is cooled to 60 ° C., charged with 14.2 parts of acrylic acid, 0.1 part of triphenylphosphine and 0.5 part of methoquinone, and replaced the nitrogen inlet with an air bubbling device to bring air into the reaction solution. The mixture was stirred while bubbling, and the temperature was raised to 110 ° C. and allowed to incubate for 9 hours to obtain Resin 3 having a resin solid content of 50% (Table 1). In addition, the weight average molecular weight (polystyrene conversion value by GPC) was 20,000, and the calculated molecular weight per acrylic group was 250.

<Synthesis Example 4>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, 48.7 parts butyl acetate, 25.4 parts GMA, polystyrene macromonomer (trade name “AS-6” Toagosei Co., Ltd.) 10.9 parts and 1.5 parts of AIBN were charged and stirred, and the temperature was raised to 90 ° C. in a nitrogen stream, followed by reaction for 10 hours. After completion of the reaction, the reaction solution is cooled to 60 ° C., charged with 12.9 parts of acrylic acid, 0.1 part of triphenylphosphine and 0.5 part of methoquinone, and replaced the nitrogen inlet with an air bubbling device to bring air into the reaction solution. The mixture was stirred while bubbling, and the temperature was raised to 110 ° C. and reacted for 9 hours to obtain a resin 4 having a resin solid content of 50% (Table 1). The weight average molecular weight (polystyrene equivalent value by GPC) was 40,000, and the calculated molecular weight per acrylic group was 275.

<Synthesis Example 5>
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet was charged with 49.1 parts of butyl acetate, 12.9 parts of GMA, 30.0 parts of methyl methacrylate, and 1.3 parts of AIBN. Then, the temperature was raised to 90 ° C. in a nitrogen stream, and the reaction was performed for 10 hours. After completion of the reaction, it is cooled to 60 ° C., charged with 6.5 parts of acrylic acid, 0.1 part of triphenylphosphine and 0.5 part of methoquinone, the nitrogen inlet is replaced with an air bubbling device, and air is contained in the reaction solution. The mixture was stirred while bubbling, and the temperature was raised to 110 ° C. and allowed to incubate for 9 hours to obtain Resin 5 having a resin solid content of 50% (Table 1). The weight average molecular weight (polystyrene converted value by GPC) was 30,000, and the calculated molecular weight per acrylic group was 545.

GMA: Glycidyl methacrylate MMA: Methyl methacrylate EA: Ethyl acrylate AS-6: Polystyrene macromonomer manufactured by Toagosei Co., Ltd.

<Preparation of hard coating agent (resin composition)>
Each material was mix | blended with the prescription shown in Table 2, and it diluted so that it might become solid content 40% with methyl ethyl ketone (henceforth, MEK), and prepared the hard-coat agents T1-T9. In Table 2, all numerical values converted to solid content (units are parts by weight unless otherwise specified) are shown.
Resins 1 to 5: Active energy ray-curable resins UA-306H synthesized in Synthesis Examples 1 to 5 UA-306H: Urethane prepolymer of pentaerythritol triacrylate / hexamethylene diisocyanate (trade name: UA-306H 100% solid content Kyoeisha Chemical Co., Ltd. weight average molecular weight 1,000)
Silica fine particles: Trade name IPA-ST-L (manufactured by Nissan Chemical Industries, Ltd.) Solid content 30%
Hydrophobic surface-treated silica fine particles: A four-necked flask equipped with a stirrer, thermometer, dropping funnel, cooling condenser and vacuum distillation apparatus was charged with 100 g of IPA-ST-L and 1.5 g of hexamethylene disilazane up to 60 ° C. A silica sol which was heated and reacted for 10 hours and surface-treated with hexamethyldisiloxane was obtained. Thereafter, the solvent was replaced while dropping methyl isobutyl ketone (hereinafter referred to as MIBK) under reduced pressure (0.02 MPa) to obtain 30% solid content of MIBK-dispersed hexamethylene disilazane surface-treated silica. The dripping amount of normal hexane used for the total light transmittance of 60 g to 70% of 10 g of the mixed solution in which the weight ratio of the surface-treated silica, MIBK, and MEK was 1: 3: 6 was 18.5 g. .
Glycerin fatty acid ester: Trade name Riquemar S-100A (Riken Vitamin Co., Ltd.)
Photopolymerization initiator: trade name Irgacure 184 (manufactured by BASF) Solid content 100%

<Lamination of hard coat layer on plastic substrate>
The hard coating agents T1 to T8 prepared above were applied to one side of the plastic film substrate shown in Table 3 and Table 4 with a bar coater # 12. After drying at 80 ° C. for 60 seconds to volatilize the organic solvent, UV light (UV irradiation condition (1)) with an integrated light amount of 0 to 300 mJ / cm ² was irradiated with a high-pressure mercury lamp to be in a semi-cured state.

The tackiness, blocking resistance, and coating film elongation of the semi-cured hard coat layer of the obtained decorative film for transfer were evaluated as follows. The results are shown in Tables 3 and 4.

<Tackiness>
The semi-hardened hard coat layer was touched and evaluated according to the following criteria.
○ = Resin component does not adhere to fingers.
X = A resin component adheres to the finger.

<Blocking resistance>
A decorative film for transfer having a semi-hardened hard coat layer is cut into a size of 5 × 5 cm, a polyethylene terephthalate film is bonded to the dry film surface side, sandwiched between glass plates, and a load of 100 g / cm ² is applied. The anti-blocking property was evaluated according to the following four steps according to the degree of sticking between the dried film and the polyethylene terephthalate film after standing in a heat retaining chamber at 24 ° C. for 24 hours.
4; State that is not attached at all 3; There is a part that is not attached, and the attached part is also easily peeled off 2; Although the whole is attached, it is peeled off easily 1; The whole is attached and peeled off Difficult

<Coating elongation>
A decorative film for transfer having a semi-hardened hard coat layer is cut into a strip having a length of 100 mm and a width of 7 mm, and set in a tensile tester (model number “RTC-1250A”, Orientec Co., Ltd.) with a chuck distance of 50 mm. The test was carried out at a tensile rate of 10 mm / min under an environment of room temperature of 25 ° C. and humidity of 45% RH, and the degree of elongation until cracks occurred in the hard coat layer was measured.

<Manufacture of decorative film for transfer>
A polyester resin (product name: P-170) manufactured by Nippon Synthetic Chemical Co., Ltd. is used as a bonding layer on the semi-cured hard coat layer prepared as described above to a solid content of 30% with a mixed solvent of toluene: methyl ethyl ketone = 1: 1. The diluted one was applied to a dry film thickness of about 1 μm using a bar coater and dried at 100 ° C. for 60 seconds to obtain a decorative film for transfer.
<In-mold injection molding>
Place each of the above decorative films for transfer created in the mold, injection mold a melt of a thermoplastic resin (trade name Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd.), and transfer the hard coat layer to the outermost surface. A molded product was obtained. Thereafter, the molded product was irradiated with UV light having an integrated light amount of 300 mJ / cm ^{2 with} a high-pressure mercury lamp (UV irradiation condition (2)) to completely cure the hard coat layer.

The pencil hardness and scratch resistance of the fully cured hard coat layer of the decorative film for transfer were evaluated as follows. The results are shown in Tables 3 and 4.

<Peel strength>
A cellophane tape (Nichiban Co., Ltd., ELPACK LP-24) with a width of 24 mm is attached to the hard coat layer side of the created decorative film for transfer, and a cut is made along the edge of the cellophane tape with a cutter, and a predetermined length. Further, the plastic film substrate and the hard coat layer were peeled off, and the peel strength was measured with a spring gauge.

<Pencil hardness>
The in-mold injection molding produced was evaluated. The test was conducted according to the test method of JIS-K-5600. A pencil hardness of 2H has an excellent hard coat property. On the contrary, a pencil hardness of H can be used as a hard coat agent, but it is slightly inferior to a hard coat property. Pencil hardness F has a hard coat property. Judged to be clearly inferior.

<Abrasion resistance>
The in-mold injection molding produced was evaluated. Using # 0000 steel wool, a load of 500 g / cm ² was applied, the cured film surface was scratched 10 times, and the presence or absence of scratches was confirmed by visual observation, and evaluated as follows.
○ = No scratch × = Scratch

PET: Polyethylene terephthalate film PC: Polycarbonate film ABS: Acrylonitrile / butadiene / styrene copolymer resin film AC: Acrylic resin film

Exfoliated PET: Thermosetting melamine resin by bar coater coating on one side of polyethylene terephthalate film (the side on which the hard coat layer will be laminated later) Trade name: TCM-01 Medium (DIC Corporation) to a dry film thickness of 1 μm A PET base material coated and heat-dried at 80 ° C. for 60 seconds to form a release layer.

Claims (3)

A decorative film for transfer having a hard coat layer,
The hard coat layer is formed by contacting a base film with a resin composition semi-cured by active energy rays,
The resin composition contains an active energy ray-curable resin (A) and a photopolymerization initiator (B),
The active energy ray-curable resin (A) is a polyfunctional (meth) acrylate having a weight average molecular weight of 10,000 to 100,000 and a molecular weight of 200 to 400 per (meth) acryloyl group. Decorative film for transfer. The active energy ray-curable resin (A) is a reaction product obtained by reacting a radical polymer of a monomer component containing at least an epoxy group-containing (meth) acrylate monomer with an α, β-unsaturated carboxylic acid. The decorative film for transfer according to claim 1, wherein the decorative film for transfer is provided. The decorative film for transfer according to claim 1 or 2, wherein the peel strength between the substrate film and the hard coat layer is 30 to 500 mN / 24 mm.