JP6233691B2 - Resin composition, active energy ray-curable hard coating agent containing the same, and decorative film - Google Patents

Description

The present invention relates to a resin composition, an active energy ray-curable hard coat agent containing the resin composition, and a decorative film.

In recent years, the surfaces of plastic injection molded products such as mobile phone terminals, personal computer housings, and car interior trims are inherently susceptible to scratching, so that they are given functionalities such as hard coat properties such as hardness and scratch resistance, and chemical resistance. A surface protective layer is provided. For this surface protective layer, active energy ray-curable resins are favored for their characteristics over thermoplastic resins and thermosetting resins. Conventionally, a surface protective layer was created on the surface of the molded product by spray painting or printing, but a plastic film with a laminated surface protective layer was placed in the mold and the molten resin was injected into the mold. Thus, an in-mold molding method in which a surface protective layer is applied to the surface of a molded product at the same time as molding has attracted attention in recent years because it is highly productive and can impart high design properties such as complex patterns.

The plastic film used for in-mold molding is called a decorative film, which is a plastic film substrate with a surface protective layer, pattern ink layer, adhesive layer, etc. made of an active energy ray-curable resin composition laminated in multiple layers. is there. Since the active energy ray-curable resin composition is generally liquid at room temperature, it has a tack (adhesiveness) immediately after coating. Therefore, when it is wound into a roll, it is in a solid state (tack-free state). There must be. If the tack-free state is not sufficient, the coated surface and the substrate surface are in close contact with each other and are not easily peeled off (referred to as blocking), resulting in problems in the subsequent steps.

Patent Document 1 discloses an acrylic resin obtained by reacting (meth) acrylic acid with a copolymer of (meth) acrylic acid glycidyl ester and an unsaturated compound having one polymerizable unsaturated bond in one molecule. An active energy ray-curable resin composition comprising a photopolymerizable monomer having two or more photopolymerizable unsaturated bonds in one molecule and a melting point of 40 ° C. or higher and a photopolymerization initiator having a melting point of 40 ° C. or higher. Is described that the surface of the coating film becomes tack-free after volatilization of the solvent, but the blocking resistance is poor.

In Patent Document 2 and Patent Document 3, proposals using thermal crosslinking between an active energy ray-curable resin having a hydroxyl group and a polyisocyanate compound have been made. In addition to poor storage stability, There is a tendency to reduce hard coat properties and blocking properties.

Patent Document 4 proposes a resin composition that uses two types of resins having different SP values and forms fine irregularities on the surface by using phase separation to impart blocking resistance. Transparency is impaired and there is a problem in design.

Patent Document 5 reports a technique for forming irregularities on the surface of the hard coat layer with inorganic fine particles, but the precipitation of the inorganic fine particles, the transmittance of the coating film, and the haze tend to decrease. In particular, silica filler is often used as an anti-blocking agent. However, a large amount of silica filler is necessary to exhibit anti-blocking property, which is also a cause of high cost.

Thus, a resin composition capable of forming a coating film having high hard coat properties and transparency while having excellent blocking resistance at low cost has not been developed yet.

Japanese Patent Application Laid-Open No. 11-1000041 JP-A-10-58895 JP 2011-143719 A JP 2007-182519 A JP 2004-42653 A

The present invention can form a semi-cured coating film that achieves both excellent blocking resistance and coating film elongation at low cost, and has excellent scratch resistance and hardness when completely cured by active energy rays. An object of the present invention is to provide a resin composition that can be applied to the surface of a molded product to form a highly transparent coating film.

As a result of diligent research, the present inventors made silica fine particles into a specific hydrophobic surface treatment state to obtain an active energy ray resin composition comprising a polyfunctional (meth) acrylate having a specific molecular weight and a photopolymerization initiator, and a plastic group. After coating on a material, when it was made into a semi-cured state with an active energy ray, it was found that it had excellent blocking resistance, and the present invention has been achieved.
That is, the present invention includes hydrophobic silica fine particles (A), a polyfunctional (meth) acrylate (B) having a weight average molecular weight of 10,000 to 200,000, and a photopolymerization initiator (C). A): methyl isobutyl ketone: methyl ethyl ketone: normal hexane = 1: 3: 6: 10 (weight blending ratio) The total light transmittance is 60 to 99%. (Hereinafter referred to as the present invention 1).

The present invention 2 is the invention 1, wherein the hydrophobic silica fine particles (A) are surface-treated with one or more compounds selected from a disiloxane compound, a disilazane compound, and a monoalkoxysilane compound. Is a resin composition having a thickness of 1 to 100 nm.

The present invention 3 is the invention 1 or 2, wherein the polyfunctional (meth) acrylate (B) is substituted with an α, β-unsaturated carboxylic acid on the radical polymer of the monomer component containing the epoxy group-containing (meth) acrylate monomer. It is a resin composition obtained by reacting and having a molecular weight of 200 to 400 per (meth) acryloyl group.

The present invention 4 is an active energy ray-curable hard coat agent containing the resin composition of any one of the present inventions 1 to 3.

The present invention 5 is a coated film in which the hard coating agent of the present invention 4 applied to a base film is irradiated with an active energy ray to form a semi-cured hard coat layer.

This invention 6 is a decorating film which formed the hard-coat layer of the semi-hardened state by irradiating an active energy ray to the hard-coat agent of this invention 4 apply | coated to the base film.

According to the present invention, it is possible to form a semi-cured coating film having both excellent blocking resistance and coating film elongation at low cost. Moreover, when it hardens | cures completely by an active energy ray, the outstanding scratch resistance and hardness can be provided to the molding surface, and the coating film which has high transparency can be formed.

The resin composition of the present invention comprises hydrophobic silica fine particles (A) (hereinafter also referred to as “component A”), polyfunctional (meth) acrylate (B) having a weight average molecular weight of 10,000 to 200,000) (hereinafter, Hydrophobic silica fine particles (A): methyl isobutyl ketone: methyl ethyl ketone: normal hexane = 1: 3: photopolymerization initiator (C)) (hereinafter also referred to as “C component”). The total light transmittance of a solution (mixture) obtained by mixing 6:10 (weight blend ratio) is 60 to 99%. Here, the total light transmittance is a transmittance when a quartz cell filled with the above-mentioned mixed solution is measured when an empty quartz cell having a thickness of 1 cm is used as a control as a total light transmittance of 100%. It is measured using a meter (HM-150 model manufactured by Murakami Color Research Laboratory). If the silica particles are insufficiently surface-treated, they aggregate in the presence of normal hexane, so that the total light transmittance is lowered. On the other hand, if the surface treatment is sufficient, high total light transmittance can be maintained without agglomeration even in the presence of normal hexane. Methyl isobutyl ketone and methyl ethyl ketone were used as dispersion solvents. If the total light transmittance is 60 to 99%, one of the excellent characteristics of the present invention can be obtained, and if it is less than 60%, the blocking resistance is insufficient.

The component (A) is obtained by treating the raw silica fine particles with a surface treatment agent to impart hydrophobicity. The raw material silica fine particles are not particularly limited, and both dry silica (also referred to as fumed silica) obtained by vaporizing silicon halide and vapor phase reaction and wet silica produced from water glass can be used. it can.

The average particle size of the component (A) is preferably 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 surface treatment agent is not particularly limited as long as it can impart hydrophobicity to the raw silica fine particles. For example, saturated fatty acid, unsaturated fatty acid, surfactant, disiloxane compound, disilazane compound, silane coupling agent And titanate coupling agents. Preferably, it is at least one compound selected from a disiloxane compound, a disilazane compound, and a silane coupling agent. As a result, the surface of the silica fine particles, which are generally hydrophilic, can be sufficiently altered to be hydrophobized, and a coating film having extremely excellent blocking resistance can be formed.

Specific examples of the disiloxane compound include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexabutyldisiloxane, hexapentyldisiloxane, hexahexyldisiloxane, hexacyclohexyldisiloxane, hexaphenyldisiloxane, Examples include 1,1,3,3-tetramethyldisiloxane, 1,3-diphenyl-1,1,3,3-tetramethylpropanedisiloxane, and 1,3-divinyltetramethyldisiloxane. Among these, hexamethyldisiloxane is particularly preferable because it is easily available.

Specific examples of the disilazane compound include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyl. Tetramethyldisilazane is mentioned. Among these, hexamethyldisilazane is particularly preferable because it is easily available.

Among the silane coupling agents, preferably a monoalkoxysilane coupling agent, specific examples include butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, Examples include phenyltrimethoxysilane, diphenyldimethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane, and diphenyldiethoxysilane. Of these, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxysilane are particularly preferable in terms of high reactivity and hydrophobicity imparting effects.

A known surface treatment method can be used for the surface treatment. For example, after the surface treatment agent is added to and reacted with silica fine particles dispersed in water, the surface dispersed in the organic solvent is added by an operation of adding an amount obtained by distilling off any organic solvent while heating and distilling off water. Treated silica fine particles can be obtained.

The component (B) is not particularly limited as long as it is a polyfunctional (meth) acrylate having a weight average molecular weight of 10,000 to 200,000. When the weight average molecular weight is less than 10,000, blocking resistance is lowered. When the weight average molecular weight exceeds 200,000, the viscosity of the resin becomes too high and handling becomes difficult. A weight average molecular weight here is the value measured from molecular weight as a polystyrene conversion value by a 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 (B) is obtained by reacting a radical polymer of a monomer component containing an epoxy group-containing (meth) acrylate monomer with an α, β-unsaturated carboxylic acid, and a (meth) acryloyl group 1 A polyfunctional (meth) acrylate having a molecular weight of 200 to 400 is preferable. Thereby, a hard coat layer having high hardness and excellent scratch resistance can be obtained.

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

The component (B) 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, AY-707S, Chisso Corporation Silaplane FM-0711, FM-0721, Daicel Chemical Industries, Ltd. Examples include PLACCEL FA10L, NOF Bremer PME-4000, PSE-1300, and the like.

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 (C) is not particularly limited as long as it can initiate polymerization by generating radicals with active energy rays, and a known component can be used. Specific examples of the component (C) 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)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) etc. are mentioned. Component (C) can be used alone or in combination of two or more.

The compounding amount of the component (A), the component (B) and the component (C) in the resin composition is about 1 to 50 parts by weight of the component (A) with respect to 100 parts by weight of the resin solid content of the component (B). The component (C) is preferably about 0.1 to 10 parts by weight. By setting it as this compounding quantity, it is easy to form the hard-coat layer semi-hardened by controlling sclerosis | hardenability, and also when a hard-coat layer is hardened completely by irradiating an active energy ray, it is hard to produce a hardening defect. This also improves the blocking resistance in the semi-cured film state. The resin composition of this invention can obtain the blocking resistance outstanding with the compounding quantity smaller than the silica filler conventionally used as blocking resistance. According to this invention, it has the outstanding blocking resistance, and can suppress raw material cost. From the same viewpoint, more preferably, the component (A) is about 1 to 30 parts by weight and the component (C) is about 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin solid content of the component (B). The component (A) is about 1 to 20 parts by weight, the component (C) is about 0.5 to 3 parts by weight, the component (A) is about 1 to 10 parts by weight, and the component (C) is 0.5 to 2.5 parts by weight. It is about the weight part.

The resin composition can be blended with a leveling agent to improve coatability. In order to facilitate peeling from the substrate, polyether-modified siloxane, polyester-modified siloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, polyester-modified polymethylalkylsiloxane , Aralkyl-modified polymethylalkylsiloxane, polyether-modified hydroxyl group-containing polydimethylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, acrylic-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane acrylic copolymer , Silicone compounds such as silicon-modified acrylic, polycaprolactone diol, polycaprolactone triol, polycaprola Ton tetraol, caprolactone modified acrylic polyol, a ε- caprolactone polymer, such as caprolactone-modified (meth) acrylate can be incorporated. In order to improve light resistance, a commercially available ultraviolet absorber or the like can also be blended.

The present invention is also an active energy ray-curable hard coat agent containing the resin composition. The hard coat agent of the present invention imparts excellent scratch resistance and hardness to the surface of the molded article by containing the resin composition, and has high transparency.

A decorative film in which the hard coat agent is applied to a substrate film and irradiated with active energy rays to form a semi-hardened hard coat layer is also one aspect of the present invention.

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 hard coat layer has low tackiness and blocking resistance that prevent the resin component from adhering to the finger when the surface of the semi-cured paint film is touched, and excellent coating film elongation.

As a method of laminating a semi-cured film (hard coat layer) on the base film, it is applied by a known method and dried / or dried, and then cured by irradiation with active energy rays so as to satisfy the above-mentioned degree of curing. By doing. 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 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.

The decorative film of the present invention is not particularly limited, and can be used as a decorative film for laminate and a decorative film for transfer.

The decorative film for laminating is, for example, a decorative film having a layer structure in which a hard coat layer is laminated on one side of a plastic film substrate and a pattern ink layer, an adhesive layer, or the like is laminated on the other side. It can be decorated by sticking. It can also be used for in-mold molding called in-mold lamination.

The above decorative film for transfer is formed by forming a release layer on one side of a base film and laminating a transfer layer (a layer laminated in the order of a hard coat layer, a pattern layer, an adhesive layer, etc.) on the release layer. It is a decorative film, and the transfer layer such as a pattern ink layer, an anchor layer, an adhesive layer, a low reflection layer, an antistatic layer, an ultraviolet ray absorbing layer, a near infrared ray blocking layer, an electromagnetic wave absorbing layer, etc., to be transferred is usually semi-cured. May be laminated in any order on the hard coat layer. It can be used for in-mold molding called in-mold decoration.

The pattern ink layer contains pigments and dyes of appropriate colors in polyvinyl resins, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl sweat tar resins, cellulose resins, alkyd resins, etc. The colored 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 molding.

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 referred to as GMA), azobisisobutyronitrile (hereinafter referred to as “below”) , AIBN), 1.6 parts, was charged and stirred, and the temperature was raised to 100 ° 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 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 allowed to incubate for 9 hours to obtain Resin 1 having a resin solid content of 50%. The weight average molecular weight (polystyrene converted value by GPC) was 15,000, and the molecular weight per acrylic group was calculated to be 214. The weight average molecular weight was measured by connecting three gel permeation chromatography (manufactured by Tosoh Corporation, trade name “HLC-8220”, column: Tosoh Corporation, trade name “TSKgel superHZM-M” in series. The values obtained are shown in Table 1.

<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 the temperature was raised to 110 ° C. and allowed to incubate for 9 hours to obtain Resin 2 having a resin solid content of 50%. 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, 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 allowed to incubate for 9 hours to obtain Resin 4 having a resin solid content of 50%. The weight average molecular weight (polystyrene equivalent value by GPC) was 40,000, and the calculated molecular weight per acrylic group was 275.

GMA: Glycidyl methacrylate AS-6: Polystyrene macromonomer manufactured by Toagosei Co., Ltd.

<Preparation of silica fine particles S1>
In a three-necked flask equipped with a stirrer, thermometer, and vacuum distillation apparatus, 500 g of isopropyl alcohol (hereinafter, IPA) -dispersed silica sol (Nissan Chemical Industries, Ltd., trade name: IPA-ST-L silica content 30%) 30 g of hexamethyldisiloxane was added as a surface treatment agent and reacted at 60 ° C. for 10 hours with stirring to obtain a hexamethyldisiloxane surface-treated silica sol. Thereafter, the flask was concentrated by distillation under reduced pressure until the flask content reached 250 g, and then 250 g of methyl isobutyl ketone (hereinafter referred to as MIBK) was added. and solvent substitution was obtained MIBK dispersion hexamethyldisiloxane surface treated silica sol (silica particle) S1 (silica content 30%, IPA content of 0.6% or less, a number average particle diameter of about 50 n m) of. Further, MIBK and methyl ethyl ketone (hereinafter referred to as MEK) were added to the obtained silica fine particles S1 to prepare 10 g of a mixed solution of silica: MIBK: MEK = 1: 3: 6 (weight mixing ratio). The amount of normal hexane required for the total light transmittance of 10 g of this mixed solution to reach 60% was 30 g. When the hexamethyldisiloxane surface-treated silica fine particles were 1, the total light transmittance was 76% when the solvent ratio was adjusted to MIBK: MEK: normal hexane = 3: 6: 10.

<Preparation of silica fine particles S2 to S7>
In the same procedure, the type of IPA-dispersed silica sol, the type of surface treatment agent and the blending amount were changed, and silica fine particles of S2 to S7 were obtained in the same procedure.

IPA-ST: Isopropyl alcohol-dispersed silica sol (particle size: about 15 nm)
IPA-ST-L: Isopropyl alcohol-dispersed silica sol (particle size: about 50 nm)
IPA-ST-ZL: Isopropyl alcohol-dispersed silica sol (particle size: about 100 nm)

<Preparation of hard coating agent (resin composition)>
Each material was mix | blended with the prescription shown in Table 3, and it diluted so that it might become solid content 40% with MEK, and prepared the hard-coat agent. In Table 2, all numerical values converted to solid content (units are parts by weight unless otherwise specified) are shown.

<Preparation of coated film>
The hard coat agents T1 to T8 prepared above were coated on one side of polyethylene terephthalate (hereinafter referred to as PET) with a bar coater # 12. After drying at 80 ° C. for 60 seconds to volatilize the organic solvent, a coated film is produced by irradiating UV light (UV irradiation condition (1)) with an integrated light amount of 0 to 300 mJ / cm ^{2 with} a high-pressure mercury lamp. did.

The tack property, blocking resistance, and coating film elongation of the semi-cured hard coat layer of the obtained coated film 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 part that is attached is easily peeled off 2; It was determined that difficulty evaluation 3 was low blocking resistance, and evaluation 4 was more excellent and low blocking resistance, and those having an evaluation of 3 or more had blocking resistance. On the other hand, evaluation 2 is inferior to blocking resistance, evaluation 1 is said to be in a state with extremely high blocking resistance, and evaluation of 2 or less was evaluated as having no blocking resistance.

<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.

<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. When the peel strength is 30 to 500 mm N / 24 mm, the substrate film and the hard coat layer can be handled without being peeled during transport into the mold, and at the same time as the transfer, the substrate film is peeled off from the hard coat layer. It can be used without peeling unevenness.

<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 using a bar coater to 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>
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.

<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

PE3A: pentaerythritol triacrylate synthetic mica: average particle size 100 nm

Claims (5)

Hydrophobic silica fine particles (A), a polyfunctional (meth) acrylate (B) having a weight average molecular weight of 10,000 to 200,000 and a photopolymerization initiator (C), the hydrophobic silica fine particles (A): methyl isobutyl ketone: methyl ethyl ketone: n-hexane = 1: 3: 6:. 10 (weight mixing ratio) of the total light transmittance of 60 to 99% der of the mixed solution is, hydrophobic silica fine particles (a) disiloxane compound, disilazane compound and a resin composition, characterized in der Rukoto those surface treated with at least one compound selected from the monoalkoxysilane compounds. The resin composition according to claim 1, wherein the hydrophobic silica fine particles (A) have a particle diameter of 1 to 100 nm. The polyfunctional (meth) acrylate (B) is obtained by reacting a radical polymer of a monomer component containing an epoxy group-containing (meth) acrylate monomer with an α, β-unsaturated carboxylic acid. 3. The resin composition according to claim 1 or 2, wherein the molecular weight per acryloyl group is 200 to 400. An active energy ray-curable hard coat agent comprising the resin composition according to claim 1. The decorative film which formed the hard-coat layer of the semi-hardened state by irradiating an active energy ray to the hard-coat agent of Claim 4 apply | coated to the base film.