TWI624371B - Transfer decorative film - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative film for transfer at a low cost, which can be formed by in-mold injection molding while transferring a decorative method without performing a previously necessary step of forming a release layer on a substrate film. The optimum peel strength is adjusted so that the base film and the transfer layer are not easily peeled off during transportation or the like, and the transfer layer can be uniformly peeled off from the base film at the time of transfer molding. Further, another object of the present invention is to provide a decorative film for transfer which can impart excellent scratch resistance and hardness to the surface of a molded article if the hard coat layer is completely cured by active energy rays.

In order to achieve the above object, the decorative film for transfer of the present invention has a hard coat layer, and the decorative film for transfer is characterized in that the hard coat layer is a resin composition which is semi-hardened by active energy rays and The resin composition includes an active energy ray-curable resin (A) and a photopolymerization initiator (B) having a weight average molecular weight of 10,000 to 100,000. Further, each (meth)acrylonitrile group has a polyfunctional (meth) acrylate having a molecular weight of 200 to 400.

Description

Transfer decorative film

The present invention relates to a decorative film for transfer. More specifically, the present invention relates to a transfer decorative film used in an in-mold injection molding simultaneous transfer decoration method, and the in-mold injection molding simultaneous transfer decoration method is used for The surface of the plastic molded article imparts functionality or designability and the like.

A manufacturing method for imparting a design such as a pattern design or a texture or a scratch (hard coating property) to a surface of a plastic product has conventionally used an in-mold injection molding method for inserting a decorative film into a mold and The injection molding is carried out by adhering to a molded article which is formed by laminating an adhesive layer, a pattern design layer, or a hard coat layer on a plastic film such as PET (polyethylene terephthalate).

Such an in-mold injection molding method can be classified into an injection molding simultaneous transfer decoration method and an injection molding simultaneous laminate decoration method depending on the difference in the composition of the decorative film adhered to the resin molded article.

The injection molding simultaneous transfer decoration method is characterized in that a release layer is formed on one side of a base film and a transfer layer is laminated on the release layer (layered in the order of a hard coat layer, a pattern design layer, an adhesive layer, etc.) After obtaining the decorative film for transfer, the decorative film for transfer is inserted into the mold, and the base film side is placed in close contact with the inner surface of the mold. After the mold is closed, the molten thermoplastic resin is After the transfer layer side is injected and filled in the mold, when the mold is opened to take out the molded product, the release layer and the hard coat layer are peeled off, and the transfer layer is transferred to the outermost surface to obtain a molded article. Such an injection molding simultaneous transfer decoration method has a peeling unevenness at the interface between the hard coat layer and the peeling layer at the time of transfer, and the interface between the release layer and the hard coat layer is liable to be peeled off during transport. When the decorative film for transfer is used, the release layer and the hard coat layer are peeled off.

In view of this, there has been proposed a transfer decorative film in which a release layer, a protective layer, a colored layer, and an adhesive layer are sequentially laminated on a substrate, and the protective layer is composed of a polymerizable (methyl group). a cured product of an ionizing radiation-hardening resin composition of an oligomer, and a peeling strength between the release layer and the protective layer after transfer is 0.1 to 1.0 N/ 25 mm (see, for example, Patent Document 1). Further, there is also proposed a hard coat transfer foil which is provided with a release layer, a hard coat layer and an adhesive layer provided on one surface of the substrate, wherein the release layer is a melamine resin. Further, the hard coat layer contains a cured product of an epitaxial radiation curable resin and a polyethylene wax (see, for example, Patent Document 2).

However, the decorative film for transfer having such a release layer causes a deterioration in cost due to the necessity of laminating a release layer, and causes a decrease in production efficiency due to an increase in the number of steps required for manufacturing.

Further, in the hard coat transfer foil disclosed in Patent Document 2, there is a problem that the adhesion between the hard coat layer and the molded product is lowered, and when the molded article is simultaneously decorated with the hard coat layer and the pattern ink layer, There is a problem that the adhesion between the hard coat layer and the pattern ink layer is deteriorated.

As described above, in the simultaneous injection molding method, it is desired to develop a decorative film for transfer, in which the transfer layer (hard coat layer, pattern design layer, and adhesive layer) is easily peeled off from the base film, and is hard. The coating layer and the pattern design layer are not peeled off, and the injection molding can be easily and inexpensively performed, and the transfer layer is used for imparting hard coating property, decoration, and the like.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open Publication No. 2011-8421

Patent Document 2: JP-A-2008-6708

An object of the present invention is to provide a decorative film for transfer which is fired in a mold In the simultaneous molding transfer printing method, the step of forming a release layer on the base film which is previously necessary is not required, and the interface between the base film and the hard coat layer can be easily peeled off at the time of transfer, and It has excellent coating film elongation, and the hard coating after complete hardening has excellent scratch resistance and hardness.

The inventors of the present invention have carefully studied and obtained the following findings: by controlling the resin composition and hardenability of the hard coat layer, the peel strength of the interface between the base film and the hard coat layer can be set even without the release layer. In the appropriate range. That is, the present invention is a decorative film for transfer having a hard coat layer, and the transfer decorative film is characterized in that the hard coat layer is a resin composition and a base which are semi-hardened by active energy rays. The resin composition includes an active energy ray-curable resin (A) (hereinafter, also referred to as "(A) component") and a photo-polymerization initiator (B). Hereinafter, also referred to as "(B) component"), the active energy ray-curable resin (A) has a weight average molecular weight of 10,000 to 100,000 and a molecular weight of each (meth)acrylonitrile group of 200 to 400. Polyfunctional (meth) acrylate. (hereinafter, referred to as "the present invention 1").

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

The decorative film for transfer according to the invention of claim 1 or 2, wherein the peeling strength between the base film and the hard coat layer is 30 to 500 mN/24 mm.

According to the present invention, a decorative film for transfer can be obtained at a low cost, and in the in-mold injection molding and transfer printing method, it is not necessary to carry out the previously necessary step of forming a release layer on the base film. It can be adjusted to an optimum peel strength which is not easily peeled off during transfer or the like, and the transfer layer can be uniformly peeled off from the base film during transfer molding, and if By hardening the hard coat layer completely by active energy rays, it is possible to impart excellent scratch resistance and hardness to the surface of the molded article.

[Best Embodiment of the Invention]

The decorative film for transfer of the present invention is used in an in-mold injection molding simultaneous transfer decoration method for imparting functionality or designability to the surface of a plastic molded article. In the decorative film for transfer of the present invention, a hard coat layer is formed adjacent to the base film, and a peeling layer which is previously required is not required between the base film and the hard coat layer.

The hard coat layer is a semi-cured material obtained by using an active energy ray to form a resin composition (hard coating agent) containing the component (A) and the component (B).

The above component (A) is a polyfunctional (meth) acrylate having a molecular weight of from 200 to 400 and a weight average molecular weight of from 10,000 to 100,000 per (meth)acrylonitrile group. When the molecular weight of each (meth) acrylonitrile group is less than 200, it is difficult to actually carry out the synthesis, and when it exceeds 400, the hard coating property is lowered, and the surface of the molded article is likely to be scratched. The molecular weight of each (meth) acrylonitrile group is preferably from 200 to 300. When the weight average molecular weight is less than 10,000, the peel strength is increased to make peeling of the base film and the hard coat layer difficult, and the surface tack is large, resulting in deterioration of anti-blocking property. If it is more than 100,000, the viscosity of the resin becomes too high and it is difficult to handle. The weight average molecular weight is preferably from 100,000 to 90,000. Here, the "weight average molecular weight" is a value obtained by measuring a weight average molecular weight obtained by gel permeation chromatography (GPC) from a polystyrene equivalent value. Further, the molecular weight of each (meth) acrylonitrile group is a value calculated from the weight average molecular weight of the {(A) component / the total of the acryl thio groups.

The above component (A) is preferably a reaction product obtained by reacting an α,β-unsaturated carboxylic acid with a radical polymer of a monomer component, the monomer component containing at least an epoxy group-containing (methyl) group. Acrylate monomer. With this, A hard coating having high hardness and excellent scratch resistance can be obtained.

The "epoxy group-containing (meth) acrylate monomer contained in the monomer component" means a compound having at least one epoxy group and one unsaturated double bond in the molecule. Specific examples thereof include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and ethylene monoxide. Cyclohexene (i.e., 1,2-epoxy-4-vinylcyclohexane) and the like. Among these, from the viewpoint of availability and raising cost, glycidyl (meth)acrylate is preferred.

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

Examples of the copolymerizable monomer include (meth) acrylate, styrene, vinyl acetate, (meth) acrylamide, and acrylonitrile; and an unsaturated double bond at the terminal on either side and does not contain A macromonomer such as an epoxy group or a carboxyl group. One or two or more of these may be contained as a monomer component.

Specific examples of the above-mentioned macromonomer include, for example, giant monomers AA-6 or AB-6, AY-707S manufactured by East Asia Synthetic Co., Ltd.; Silaplane FM-0711, FM-0721 manufactured by Chisso Co., Ltd.; PLACEL FA10L made by Daicel Chemical Industry Co., Ltd.; Blemmer PME- made by Nippon Oil Co., Ltd. 4000, PSE-1300, etc.

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

The component (B) can be used without any particular limitation as long as it can generate a radical by the active energy ray. Specific examples of the component (B) include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, and 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one 2-hydroxyl 1-{4-[4-(2-hydroxy-2-methyl-propenyl)benzyl}phenyl}-2-methyl-propan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)propan-1-one, 2-benzyl-2-dimethylamino-1- (4-(N-morpholinyl)phenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholinyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzylidene- Diphenyl-phosphine oxide, 4-methyldiphenyl ketone, 1-[4-(4-benzylidylphenylthio)phenyl]-2-methyl-2-(4-methylbenzene Sulfosyl)propan-1-one, 1,2-octanedione, 1-[4-(phenylthio), 2-(O-benzylidenehydrazide)] {1,2- Octanedione, 1-[4-(phenylthio), 2-(O-benzoyloxime)]}, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]-1-(O-acetamidopurine) {ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)} Wait. (B) The components may be used singly or in combination of two or more.

In the above resin composition, the amount of the component (A) and the component (B) is preferably from 0.1 to 10 parts by weight based on 100 parts by weight of the resin component of the component (A). By setting this amount, it is easy to control the hardenability to form a semi-hardened hard coat layer, and when the active energy ray is irradiated after the transfer to completely harden the hard coat layer, hardening failure is less likely to occur.

The above resin composition may be formulated with an inorganic filler for the purpose of improving wear resistance or improving blocking resistance. As the inorganic filler, a conventional one such as silica fine particles or metal oxide fine particles can be used without particular limitation. Examples of the metal oxide fine particles include titanium oxide, aluminum oxide, cerium oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, and indium oxide. These may be used alone or in combination of two or more. Among these, fine particles of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide are preferred from the viewpoint that the commercial product group is abundant, easily available, and inexpensive. Further, from the viewpoint of providing a decorative film for transfer having excellent blocking resistance, it is particularly preferred to apply surface-treated cerium oxide fine particles. In the case where an inorganic filler is formulated in a resin composition Preferably, the inorganic filler is from about 1 to 30 parts by weight based on 100 parts by weight of the resin solid content of the component (A). When it is set in this range, it can be set as the decorative film for transcription|transfer which has the outstanding anti-blocking property.

The above surface-treated cerium oxide is preferably a hydrophobic surface-treated cerium oxide microparticle, which is obtained in 10 g of a mixed solution of cerium oxide microparticles: methyl isobutyl ketone: methyl ethyl ketone = 1:3:6. When the total light transmittance of the solution obtained by adding n-hexane is 60 to 70%, the amount of n-hexane to be dropped is 10 g or more. When it is set in this range, the decorative film for transfer which is excellent in blocking resistance can be obtained.

The above inorganic filler is preferably one which has an average particle diameter of about 1 to 200 nm (by laser diffraction/scattering method). When the average particle diameter is less than 1 nm, the storage stability is not good, and when the average particle diameter is more than 200 nm, there is a concern that the cured film is likely to be whitened, and the optical properties such as haze or transmission efficiency are likely to be impaired. The average particle diameter is more preferably from 1 to 100 nm.

In the decorative film for transfer of the present invention, when the monomer component of the raw material of the component (A) contains the macromonomer, and/or the resin composition contains the hydrophobic surface ceria particles. It is particularly excellent in blocking resistance and is therefore preferred.

The resin composition may be formulated with a leveling agent or an antifoaming agent for the purpose of improving coatability, for the purpose of improving light resistance. A commercially available ultraviolet absorber may be blended, and a glycerin fatty acid ester, a polyglycerin fatty acid ester, a sorbitan fatty acid ester, a fatty acid decylamine or the like may be formulated for the purpose of adjusting the peel strength from the base film.

The substrate film is not particularly limited, and for example, polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triethyl fluorenyl cellulose resin, ABS (acrylonitrile-butadiene-styrene) resin, AS (acrylonitrile-styrene) resin, norbornene-based resin, and the like.

In the present invention, the hard coat layer formed adjacent to the base film is obtained by semi-hardening the resin composition by active energy rays.

The above-mentioned "semi-hardening" means that an unreacted (meth) acrylonitrile group remains after a crosslinking reaction of a part of the (meth) acryl fluorenyl group in the active energy ray-curable resin. status. Which means that the use of infrared spectroscopy (infrared spectroscopy) measurement was measured by attenuated total reflection measurement method (ATR, Attenuated Total Reflection), the wavelength of the peak area P1620 vicinity of 1620cm ^-1, a wavelength near the peak area 1720cm ^-1 The degree of hardening represented by the following formula (1) obtained by the value of P1720 (P1620/P1720) is 0.7 or more and 0.95 or less.

Hardening degree = (P1720 after UV irradiation / P1720 after UV irradiation) / (P1620 before UV irradiation / P1720 before UV irradiation)

The semi-hardened resin composition described above has low tackiness and blocking resistance, and excellent coating film elongation, and the low viscosity is that the resin component does not adhere when the surface of the semi-hardened coating film is touched with a finger. On the finger.

The method of laminating a semi-cured film (hard coat layer) on the above-mentioned base film is carried out by coating and drying by a conventional method; or by irradiating an active energy ray after drying to be hardened to satisfy the above hardening. degree. Examples of the coating method of the hard coating agent include, for example, bar coater coating, Meyer bar coating, air-knife coating, and gravure coating ( Gravure coating), reverse gravure coating, offset printing, flexo printing, screen printing method, and the like. Further, the coating amount is not particularly limited, and usually, the weight after drying is in the range of 0.1 to 20 g/m ² , preferably in the range of 0.5 to 10 g/m ² .

The decorative film for transfer may have a pattern ink layer, an anchor layer, an adhesive layer, a low reflection layer, an antistatic layer, an ultraviolet absorbing layer, and a near infrared ray shielding layer which are usually transferred in any order. A transfer layer such as an electromagnetic wave absorbing layer is laminated on the hard coat layer of the semi-cured material.

The above-mentioned patterned ink layer is obtained by laminating a colored ink by using a printing method in which a pigment or a dye of an appropriate color is blended with a polyvinyl resin, a polyamide resin, a polyester resin, and a poly Acrylic resin And a polyurethane resin, a polyvinylacetal resin, a cellulose resin, an alkyd resin, etc., the printing method is gravure coating, reverse gravure coating Cloth, offset printing, screen printing, etc. The ink layer of the pattern may be monochromatic or multi-colored. In addition, metal evaporation can also be carried out in a comprehensive or partial manner.

In order to improve the adhesion between the transfer layers, for example, a two-layer curable urethane resin, a melamine or an epoxy thermosetting resin, a vinyl chloride resin, or a polyacrylic resin can be used. A thermoplastic resin is laminated by a conventional printing method.

The adhesive layer is required to adhere the transfer layer to the surface of the molded article. The above adhesive layer is used to laminate the full-area layer or only the layer to be transferred. As the adhesive layer, one or two or more kinds of suitable ones such as a polyacrylic resin, a polystyrene resin, a polyamide resin, and an indene resin can be used depending on the material of the molded product.

The above-mentioned decorative film for transfer can be used for in-mold injection molding and transfer printing. For example, the transfer decorative film is continuously conveyed to a mold composed of a fixed mold and a movable mold by using a conveyance roller or the like, and the base film side is brought into contact with the fixed mold surface, and the movable mold is moved after appropriately adjusting the position. And mold clamping. Further, a thermoplastic resin which has been previously melted by heat is injected into the mold from the transfer layer side of the decorative film for transfer under high temperature and high pressure, and then quenched and then opened, and the mold is turned. The molded layer on which the printing layer has been transferred to the outermost surface is taken out.

Preferably, the peel strength between the base film and the hard coat layer is 30 to 500 mN/24 mm. Since the peeling strength is set to be within this range, when it is conveyed toward the inside of the mold, the treatment can be performed without causing peeling of the base film and the hard coat layer, and the base film is peeled off from the hard coat layer while being transferred. In this case, it is possible to produce an excellent transferability without causing peeling unevenness. More preferably, it is 40 to 300 mN/24 mm, and further preferably 50 to 200 mN/24 mm.

"Embodiment"

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. In addition, in each case, unless otherwise stated, all "parts" and "%" are based on weight.

<Preparation of active energy ray-curable resin (polyfunctional (meth) acrylate)> <Synthesis Example 1>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 48.6 parts of butyl acetate and 32.6 parts of glycidyl methacrylate (hereinafter referred to as "GMA") were fed. , azobisisobutyronitrile (hereinafter referred to as "AIBN") 1.6 parts, and stirred under a nitrogen gas stream In this case, after raising the temperature to 100 ° C, the reaction was carried out for 10 hours. After completion of the reaction, the mixture was cooled to 60 ° C, and 16.6 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.1 part of p-methoxyphenol (methoquinone) were fed, and the nitrogen gas inlet was replaced with an air bubbling device. While bubbling the air in the reaction liquid, the mixture was stirred, heated to 110 ° C, and subjected to a heat retention reaction for 9 hours to obtain a resin 1 having a resin solid content of 50% (Table 1). Further, the weight average molecular weight (polystyrene equivalent value obtained by GPC) was 12,000, and the molecular weight of each propylene fluorenyl group was calculated to be 214. The weight average molecular weight is a gel permeation chromatography (manufactured by Tosoh Corporation, trade name "HLC-8220") and the column (manufactured by Tosoh Corporation, trade name "TSKgel superHZ2000") 3 The values obtained by the series connection are measured.

<Synthesis Example 2>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 49.2 parts of butyl acetate, 33.0 parts of GMA, and 0.3 parts of AIBN were fed and stirred, and the temperature was raised to 85 ° C in the case of a nitrogen gas stream. The reaction was carried out for 10 hours. After completion of the reaction, the mixture was cooled to 60 ° C, and 16.8 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.5 part of p-methoxyphenol were fed, and the nitrogen gas inlet was replaced with an air bubbling device, and air was bubbled in the reaction liquid. While stirring, the temperature was raised to 110 ° C, and the heat retention reaction was carried out for 9 hours to obtain a resin 2 having a resin solid content of 50% (Table 1). Further, the weight average molecular weight (polystyrene equivalent value obtained by GPC) was 60,000, and the calculated molecular weight of each acrylonitrile group was 214.

<Synthesis Example 3>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 48.8 parts of butyl acetate, 28.0 parts of GMA, 3.5 parts of ethyl acrylate (EA), and 3.5 parts of methyl methacrylate (MMA) were fed. 1.4 parts of AIBN was stirred and heated to 90 ° C in a nitrogen gas stream, and the reaction was carried out for 10 hours. After completion of the reaction, the mixture was cooled to 60 ° C, and 14.2 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.5 part of p-methoxyphenol were fed, and the nitrogen gas inlet was replaced with an air bubbling device, and air was bubbled in the reaction liquid. While stirring, the temperature was raised to 110 ° C, and the heat retention reaction was carried out for 9 hours to obtain a resin 3 having a resin solid content of 50% (Table 1). Further, the weight average molecular weight (polystyrene equivalent value obtained by GPC) was 20,000, and the calculated molecular weight of each acrylonitrile group was 250.

<Synthesis Example 4>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 48.7 parts of butyl acetate, 25.4 parts of GMA, and a polystyrene macromonomer (trade name "AS-6" East Asia Synthetic Co., Ltd.) were fed. Company) 10.9 parts, 1.5 parts of AIBN, and stirred, and in the case of a nitrogen gas stream, the temperature was raised to 90 ° C, and the reaction was carried out for 10 hours. After completion of the reaction, the mixture was cooled to 60 ° C, and 12.9 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.5 part of p-methoxyphenol were fed, and the nitrogen gas inlet was replaced with an air bubbling device, and air was bubbled in the reaction liquid. While stirring, the temperature was raised to 110 ° C, and the heat retention reaction was carried out for 9 hours to obtain a resin 4 having a resin solid content of 50% (Table 1). In addition, The weight average molecular weight (polystyrene equivalent value obtained by GPC) was 40,000, and the calculated molecular weight of each acrylonitrile group was 275.

<Synthesis Example 5>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 49.1 parts of butyl acetate, 12.9 parts of GMA, 30.0 parts of methyl methacrylate, and 1.3 parts of AIBN were fed and stirred in a nitrogen stream. In the case of heating to 90 ° C, the reaction was carried out for 10 hours. After completion of the reaction, the mixture was cooled to 60 ° C, and 6.5 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.5 part of p-methoxyphenol were fed, and the nitrogen gas inlet was replaced with an air bubbling device, and air was bubbled in the reaction liquid. While stirring, the temperature was raised to 110 ° C, and the heat retention reaction was carried out for 9 hours to obtain a resin 5 having a resin solid content of 50% (Table 1). Further, the weight average molecular weight (polystyrene equivalent value obtained by GPC) was 30,000, and the calculated molecular weight of each acrylonitrile group was 545.

‧GMA: glycidyl methacrylate.

‧MMA: Methyl methacrylate.

‧EA: ethyl acrylate.

‧AS-6: Polystyrene giant monomer produced by East Asia Synthetic Co., Ltd.

<Preparation of Hard Coating Agent (Resin Composition)>

The materials shown in Table 2 were blended with each material, and diluted to a solid content of 40% with methyl ethyl ketone (hereinafter referred to as "MEK") to prepare a hard coating agent T1 to T9. In addition, in Table 2, the numerical value which shows all the conversion into a solid content (The unit is a weight part, when it is not specifically mentioned.

‧ Resin 1 to 5: The active energy ray-curable resin described in Synthesis Examples 1 to 5, as shown in Table 1.

‧UA-306H: urethane prepolymer of pentaerythritol triacrylate/hexamethylene diisocyanate (trade name UA-306H, solid content 100%, total It is manufactured by Wingsho Chemical Co., Ltd. and has a weight average molecular weight of 1,000).

‧ cerium oxide microparticles: trade name IPA-ST-L (manufactured by Nissan Chemical Industries Co., Ltd.), solid content is 30%.

‧ Hydrophobic surface treatment of cerium oxide microparticles: 100 g of IPA-ST-L, hexamethylene diazide nitrogen in a four-necked flask equipped with a stirrer, thermometer, dropping funnel, cooling condenser and vacuum distillation apparatus 1.5 g of hexamethylene disilazane was heated and heated to 60 ° C for 10 hours to obtain a silica sol surface-treated with hexamethylene dioxane. Then, while dropwise adding methyl isobutyl ketone (hereinafter referred to as "MIBK"), solvent substitution was carried out under reduced pressure (0.02 MPa) to obtain a surface-treated oxidized by MIBK-dispersed hexamethylene diazane. The solid content of 矽 is 30%. When the weight ratio of the surface-treated cerium oxide to MIBK and MEK is 1:3:6, the total light transmittance of 10 g of the mixed solution is 60 to 70%, and the amount of n-hexane to be used is 18.5. Gram.

‧Glycerol fatty acid ester: trade name RIKEMAL S-100A (manufactured by Riken Vitamin Co., Ltd.).

‧ Photopolymerization initiator: trade name IRGACURE 184 (manufactured by BASF Corporation), solid content is 100%.

<Lamination of hard coating for plastic substrates>

On the one surface of the plastic film substrate shown in Tables 3 and 4, the hard coating agents T1 to T9 prepared above were applied by a bar coater #12. After drying at 80 ° C for 60 seconds to volatilize the organic solvent, UV rays (UV irradiation conditions (1)) having a cumulative light amount of 0 to 300 mJ/cm ² were irradiated with a high pressure mercury lamp to make the hard coating agent semi-hardened.

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

<stickiness>

The semi-hardened hard coat was touched with a finger and evaluated on the following basis.

○=The resin component does not adhere to the fingers.

×=The resin component will adhere to the finger.

<Anti-blocking property>

The decorative film for transfer having a hard coat layer in a semi-hardened state was cut into a size of 5 × 5 cm, and a polyethylene terephthalate film was bonded to the side of the dried film, sandwiched between glass plates, and 100 g was applied. The load of /cm ² was statically placed in a 40 ° C holding chamber for 24 hours, and the blocking resistance was evaluated in the following four steps according to the adhesion of the dried film to the polyethylene terephthalate film.

4: completely unsticked state

3: There is no adhesive, and it is easy to peel off after pasting.

2: Although the whole has been pasted, it is easy to peel off

1: Overall sticking, difficult to peel off

<coating film elongation>

The transfer decorative film having a hard coat layer having a semi-hardened state was cut into a strip shape having a length of 100 mm and a width of 7 mm, and was set on a tensile tester (model number) with a chuck distance of 50 mm. RTC-1250A", Orientec Co., Ltd.) was carried out at a tensile rate of 10 mm/min at room temperature of 25 ° C and a humidity of 45% RH, and was measured until the crack of the hard coat layer occurred. degree.

<Manufacture of decorative film for transfer>

In the semi-hardened hard coat layer produced as described above, a polyester resin (trade name: P-170) manufactured by Nippon Synthetic Chemical Co., Ltd. as an adhesive layer was used as toluene: methyl ethyl ketone = 1: The mixed solvent of 1 was diluted to have a solid content of 30%, coated with a coating bar to have a dry film thickness of about 1 μm, and dried at 100 ° C for 60 seconds to obtain a decorative film for transfer.

<In-mold injection molding>

The above-mentioned respective decorative films for transfer are placed in a mold, and a melt of a molded thermoplastic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name ACRYPET VH) is injected to obtain a melt. A molded article obtained by transferring a hard coat to the outermost surface. Then, this molded product was irradiated to a molded product (UV irradiation condition (2)) with a UV light having a cumulative light amount of 300 mJ/cm ² using a high-pressure mercury lamp, so that the hard coat layer was completely hardened.

The fully hardened hard film of the decorative film for transfer is evaluated as follows The pencil hardness and scratch resistance of the coating. The results are shown in Tables 3 and 4.

<peel strength>

On the hard coat side of the manufactured decorative film for transfer, a cellophane tape (Nichiban Co., Ltd., trade name Lpack LP-24) having a width of 24 mm was adhered, and a slit was cut out along the end of the cellophane tape with a cutter. The plastic film substrate and the hard coat layer were peeled off to a specific length, and the peel strength was measured with a spring scale.

<pencil hardness>

The in-mold injection molded article produced was evaluated. This was carried out in accordance with the test method of JIS-K-5600. The pencil hardness of 2H was considered to have excellent hard coating property; on the contrary, the pencil hardness of H was judged to be a hard coating film, but the hard coating property was slightly worse; the pencil hardness F was judged to be hard. The filming property is significantly worse.

<scratch resistance>

The in-mold injection molded article produced was evaluated. A load of 500 g/cm 2 was applied using #0000 steel wool, and the surface of the cured film was rubbed back and forth 10 times to visually confirm the presence or absence of scratches, and was evaluated as described below.

○: no scars

×: There are scars

‧ PET: polyethylene terephthalate film.

‧ PC: polycarbonate film.

‧ ABS: Acrylonitrile-butadiene-styrene copolymer resin film.

‧AC: Acrylic resin film.

‧ Stripped PET: Coating a thermosetting melamine resin, TCM-01 Medium (DIC), on a single side of a polyethylene terephthalate film (the side where the hard coat layer is subsequently laminated) by coating with a coating bar A PET substrate having a release film thickness of 1 μm and thermally dried at 80 ° C for 60 seconds to form a release layer was formed.

Claims (2)

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