KR20150114462A - Film for surface decoration - Google Patents

Abstract

It is an object of the present invention to provide a surface decorative film which is capable of exhibiting sufficient smoothness at the beginning of decoration and at the same time capable of sustaining sufficient smooth running over a long period of time. The surface decorating film of the present invention is a surface decorating film having a surface decorating layer on a base film, wherein the surface decorating layer comprises a cured product of the curable resin compound and a quaternary ammonium salt type having a weight average molecular weight of 20,000 to 100,000 Of the cationic resin and at least two kinds of inorganic fine particles satisfying a predetermined condition with respect to the average particle diameter and the surface decor layer has a surface roughness SMD measured by a KES surface tester of 0.40 탆 to 2.0 탆 Or less, and is excellent in smooth transportability.

Description

{FILM FOR SURFACE DECORATION}

TECHNICAL FIELD The present invention relates to a surface decorative film capable of imparting smooth and smooth touch.

BACKGROUND ART [0002] Conventionally, the surface of various resin molded articles such as automobile interior parts, electrical product housings, building materials, and the like has been decorated with films, and various decorative films are known. However, most of them are to improve the appearance (so-called appearance) by imparting gloss, color, shape and the like, and a decorative film aimed at imparting a desired touch to the surface of the resin molded article has hardly been reported.

However, even if a desired appearance (for example, imitating solid wood) is imparted to the resin molded body, a touch feeling that is felt when actually touching is a touch feeling imagined from the appearance (for example, If it is distant from the touch, it does not fit the consumer's genuine intention and can not increase the product value sufficiently.

In the case of imparting tactile sensation to the resin molded article to increase the value of the product, the tactile feeling required for the resin molded article varies depending on the appearance and the like. For example, in the case of the appearance of a grain pattern imitating a solid wood, it is desired to have a roughly smooth tactile feel (similar to the case referred to in the present specification as " smooth running " , A moist touch similar to that of genuine leather is required. Of these various touches, the present inventor has proposed a decorative film capable of imparting tactile sensation of white wood on the surface of the resin molded article, paying attention to "smooth running". Specifically, a surface decoration layer constituted by using a water-soluble resin (A), a curing agent (B), a cationic substance (C) and a particle (D) at a predetermined ratio is provided on a base film surface, The coating amount of the layer and the bulk density are controlled to a specific range. This decorative film is intended to exhibit " smooth running " by absorbing moisture on the surface of the formed article due to hygroscopicity of the water-soluble resin itself and containing a large amount of particles to render the surface decorated layer porous structure.

Japanese Patent Laid-Open Publication No. 2118284

However, in the case of decorating the surface of the resin molded article using the surface decorative film described in Patent Document 1, sufficient smoothness of conveyance can be obtained at the beginning of decoration. However, when the molded article is used for a long period of time, . Although the cause thereof is unclear, it is presumed that the hygroscopicity which can be expressed by the water-soluble resin is limited, and that the moisture absorbed by the water-soluble resin is hardly damp-proofed.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a surface decorative film which is capable of exhibiting sufficient smoothness at the beginning of decoration and capable of sustaining a sufficient smoothness over a long period of time.

As used herein, the term " smooth-running " means a sensation that is expressed by having no sticky feeling sticking to the hand and having an appropriate density, and is made of a solid wood (specifically, painted with varnish or varnish Wood) that is not very good.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive investigations to solve the above problems and have found that a cationic resin having an average molecular weight in a specific range of not less than two kinds of inorganic fine particles hardly tacky, And two or more kinds of inorganic fine particles having an average particle diameter satisfying predetermined conditions are selected and the surface roughness SMD measured by a KES surface tester is controlled to a predetermined range capable of reproducing an appropriate density It is possible to increase the smoothness of the original decoration and to improve the durability of the decoration, thereby completing the present invention.

That is, the present invention includes the following configuration.

(1) A surface decorating film having a surface decorating layer on a base film, wherein the surface decorating layer comprises a cured product of a curable resin compound, a quaternary ammonium salt type cationic resin having a weight average molecular weight of 20,000 to 100,000, , And at least two kinds of inorganic fine particles satisfying the following conditions (i) to (iv), and the surface decoration layer has a surface roughness SMD measured by a KES surface tester of 0.40 탆 to 2.0 탆 Excellent surface decorative film with excellent smoothness.

(i) those having an average particle diameter in the range of 1.0 to 50 mu m

(ii) those having an average particle diameter different by 1.0 占 퐉 or more

(iii) the average particle diameter of the particles having the smallest average particle diameter is 1.0 μm or more and 16 μm or less

(iv) the average particle diameter of the particles having the largest average particle diameter is not less than 8 μm and not more than 50 μm

(2) The surface decorative film according to (1), wherein the surface decoration layer has a static friction index of 1.0 to 4.5, which is measured using a silicone sensor ruber with a KES surface friction tester.

(3) The surface decorative film according to the above (1) or (2), wherein the total content of the inorganic fine particles is 5 to 35 parts by mass relative to 100 parts by mass of the sum of the cured product of the curable resin compound and the cationic resin.

(4) The positive electrode active material according to any one of the above items (1) to (3), wherein the content of the particles having the smallest average particle diameter in the inorganic fine particles contained in the two or more kinds is 15% by mass or more and 85% Described surface decorative film.

(5) The catalyst according to any one of the above items (1) to (4), wherein the content of particles having the largest average particle diameter among the inorganic fine particles contained in two or more species is 15% by mass or more and 85% Described surface decorative film.

(6) The positive resist composition as described in any one of (1) to (5) above, wherein the content of the inorganic fine particles is 0.75 to 29.75 parts by mass relative to the total 100 parts by mass of the cured product of the curable resin compound and the cationic resin. Surface decorative film.

(7) The surface-ornamental composition according to any one of (1) to (6) above, wherein the quaternary ammonium salt type cationic resin is contained in an amount of 2 to 25 parts by mass based on 100 parts by mass of the cured resin composition film.

(8) The surface decorative film according to any one of (1) to (7) above, wherein the curable resin compound contains at least 5% by mass of an ionizing radiation curable resin compound having three or more functions.

According to the surface decorative film of the present invention, it is possible to express sufficient smoothness in the beginning of decoration, and to maintain sufficient smoothness for a long period of time.

Since the smooth running box in which the surface decorative film of the present invention is to be developed is a touch like the uncoated, non-coated wood, for example, when decorations such as printing a grain pattern on the outer surface are performed, It becomes a molded article, and the value of the product can be increased. In addition, since the smooth surface of the surface decorative film of the present invention is maintained for a long period of time, the value of this product is further increased.

Such a surface decorative film of the present invention is useful for, for example, a construction material application, a built-in application of a vehicle or a furniture, and various molding processing applications in which a surface is decorated using a film, For example, a housing or member of a mobile personal computer, an OA appliance or a home appliance, an automobile interior member such as an instrument panel or a handle).

The surface decorative film of the present invention has a surface decorative layer on at least one side of a base film and is a decorative film excellent in smooth transportability, giving a smooth feeling to the surface of a decorative object (resin molded article or the like).

(Surface decorative layer)

The surface decorating layer in the present invention contains a cured product of a curable resin compound, a cationic resin, and two or more kinds of inorganic fine particles, and for example, a curable resin compound, a cationic resin and two or more kinds of inorganic fine particles Is applied on a base film, followed by drying and curing treatment.

The curable resin compound refers to a raw material compound or a polymer thereof (including an oligomer) that gives a resin that is cured through a crosslinking reaction and / or a polymerization reaction by external excitation energy, and is a compound of an active ray (ultraviolet ray, radiation, electron beam, etc.) Ionizing radiation-curable resin compounds which are cured by irradiation, and thermosetting resin compounds which are cured by heat, preferably ionizing radiation-curable resin compounds. The surface decorative layer is composed of a cured product obtained by applying external excitation energy required for a curable resin compound formed in a thin film shape (layered).

As the ionizing radiation curable resin compound, there may be mentioned, for example, an ultraviolet ray curable urethane (meth) acrylate resin, an ultraviolet ray curable polyester (meth) acrylate resin, an ultraviolet curable epoxy (meth) acrylate resin, ) Acrylate ionizing radiation curable resin compounds. Of these, ultraviolet curable urethane acrylate resins are preferred.

The ionizing radiation-curable resin compound preferably contains an ionizing radiation-curable resin compound having three or more functions, and it is preferable to use a bifunctional ionizing radiation-curable resin compound in combination if necessary. As a result, the surface decoration layer can be provided with appropriate hardness and flexibility. In this case, the ionizing radiation-curable resin compound having three or more functionalities is preferably 5% by mass or more, and more preferably 10% by mass or more, of the curable resin compound. The upper limit is not particularly limited, but preferably 95% by mass or less.

When the (meth) acrylate ionizing radiation-curable resin compound is used as the ionizing radiation curable resin compound, the bifunctional (meth) acrylate ionizing radiation curable resin compound is preferably a polyhydric alcohol having two or more alcoholic hydroxyl groups in one molecule A compound having an esterified product of (meth) acrylic acid having two hydroxyl groups and the like can be used. Specifically,

(meth) acrylic acid diesters of an alkylene glycol having 2 to 12 carbon atoms such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) Neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate,

(meth) acrylate diesters of polyoxyalkylene glycols such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di Acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth)

(c) (meth) acrylic acid diesters of polyhydric alcohols: pentaerythritol di (meth) acrylate,

(meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts of hydrides of bisphenol A or bisphenol A: 2,2'-bis (4-acryloxyethoxyphenyl) propane, 2,2 ' Bis (4-acryloxypropoxyphenyl) propane, etc.,

(meth) acryloyloxy (meth) acryloyloxy group in the molecule, which is obtained by further reacting an alcoholic hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing compound obtained by previously reacting a polyvalent isocyanate compound and two or more alcoholic hydroxyl group- Urethane (meth) acrylates,

(f) epoxy (meth) acrylates having two (meth) acryloyloxy groups in a molecule obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid.

When a (meth) acrylate ionizing radiation curable resin compound is used as the ionizing radiation curable resin compound, the (meth) acrylate ionizing radiation curable resin compound having three or more functional groups may be specifically,

(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate,

(meth) acryloyl group in a molecule, which is obtained by further reacting an alcoholic hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing compound obtained by previously reacting a polyisocyanate compound (b) and two or more alcoholic hydroxyl group- Urethane (meth) acrylates having a silane group,

(c) epoxy (meth) acrylates having three or more (meth) acryloyloxy groups in the molecule, obtained by reacting a compound having three or more epoxy groups in the molecule with acrylic acid or methacrylic acid.

Examples of the thermosetting resin compound include a thermosetting urethane resin, a thermosetting acrylic resin, a thermosetting silicone resin, a thermosetting polyester resin, a thermosetting vinyl ester resin, a thermosetting epoxy resin, and a thermosetting phenol resin. Of these, a thermosetting urethane resin is particularly preferable.

Specific examples of the above-mentioned thermosetting urethane resin include, in addition to the polyester type polyurethane, the polyether type polyurethane, the polycarbonate type polyurethane and the polyether polycarbonate type polyurethane, Modified with a different polymer (for example, silicone modified, fluorinated polymer modified, polyacrylate based polymer modified), and the like.

The cationic resin to be contained in the surface decoration layer of the present invention is a quaternary ammonium salt type cationic resin having a weight average molecular weight of 20,000 to 100,000 (hereinafter also referred to as a "specific cationic resin"). By containing a specific cationic resin having a molecular weight in this specific range, the surface decoration layer exhibits high hydrophilicity, so that it is easy to absorb the moisture of the palm touching the surface decoration layer, and it helps to develop a smooth touch And at the same time, it is possible to continue the smoothly tactile sensation over a long period of time.

Examples of the quaternary ammonium salt type cationic resin to be a specific cationic resin include dimethylaminoalkyl methacrylate (for example, dimethylaminoethyl methacrylate) and dimethylaminoalkyl acrylamide (for example, (Meth) acrylic acid ester monomers (preferably methacrylic esters), and the like can be cited as the alkyl halide salt (for example, methyl acrylate salt) . Commercially available products include, for example, cationic agents such as Acrylic series manufactured by Taihe Fine Chemicals Co., Ltd., Papiogen (registered trademark) series, and Unisense series manufactured by Senkasaka.

The weight average molecular weight of the specific cationic resin is preferably 30,000 or more, more preferably 33,000 or more, preferably 90,000 or less, more preferably 80,000 or less, further preferably 77,000 or less. The weight average molecular weight of a specific cationic resin can be measured, for example, by liquid chromatography mass spectrometry.

The specific cationic resin is preferably contained in an amount of 2 parts by mass or more and 25 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the cured product of the curable resin compound. If the content of the specific cationic resin is too small, it is difficult to keep the smooth transporting property for a long period of time. If the content is too large, the surface strength may decrease or the appearance error may occur due to bleeding out of the cationic resin.

The inorganic fine particles to be contained in the surface decorating layer of the present invention are mainly used for imparting difficulty to the surface decorating layer and making it possible to realize smooth and smooth touch. By selecting and containing two or more kinds of inorganic fine particles having an average particle diameter satisfying a predetermined condition, it is possible to continue smooth running for a long period of time.

The inorganic fine particles satisfy the following (i) to (iv).

(i) those having an average particle diameter in the range of 1.0 to 50 mu m (preferably in the range of 3.0 to 30 mu m, more preferably in the range of 6.0 to 15 mu m)

(ii) an average particle diameter of 1.0 mu m or more (preferably 2.0 mu m or more, more preferably 3.0 mu m or more)

(iii) the average particle diameter of the particles having the smallest average particle diameter is 1.0 占 퐉 or more and 16 占 퐉 or less (preferably 3.0 占 퐉 to 15 占 퐉, and more preferably 6.0 占 퐉 to 13 占 퐉)

(iv) the average particle diameter of the particles having the largest average particle diameter is 8 탆 or more and 50 탆 or less (preferably 10 탆 or more and 30 탆 or less, and more preferably 12 탆 or more and 20 탆 or less)

The average particle diameter of the inorganic fine particles in the present invention means the volume average particle diameter measured by a coulter counter method.

In the present invention, when the average particle diameter of two or more inorganic fine particles is to be obtained at the same time, the average particle diameter of each particle is obtained by separating the peaks detected by overlapping. The larger the difference in average particle diameter, which is a requirement, the more preferable, and the more preferable it is 3.0 탆 or more.

The kind of the inorganic fine particles is not particularly limited and examples thereof include titanium dioxide, calcium carbonate, silicon dioxide (silica), barium sulfate, aluminum oxide, aluminum hydroxide, zeolite, zinc oxide, talc, benzoguanamine particles, Among them, silicon dioxide and talc are preferable. The shape of the inorganic fine particles is not particularly limited, and any shape such as spherical shape, flat shape, rod shape, irregular shape, and different aspect ratio can be employed. However, desirable.

In the present invention, at least two kinds of inorganic fine particles having different average particle diameters may be used, and the kind and shape of two or more kinds of inorganic fine particles may be the same or different.

The total content of the inorganic fine particles is preferably not less than 5 parts by mass and not more than 35 parts by mass, more preferably not less than 5.5 parts by mass and not more than 30 parts by mass based on 100 parts by mass of the total amount of the cured product of the curable resin compound and the specific cationic resin Or less, more preferably 6 parts by mass or more and 25 parts by mass or less. When the total content of the inorganic fine particles is too small, there is a tendency that the smooth touch feeling is insufficient. On the other hand, if the total content of the inorganic microparticles is too large, there is a tendency that unpleasant tactile sensation which is distant from the smooth running support is likely to occur. In addition, the particles tend to fall off, and the smooth touch feeling is likely to change, making it difficult to sustain smooth running for a long period of time. Further, the surface decoration layer may become fragile, and the moldability may be deteriorated.

The content per one kind of the inorganic fine particles is preferably 0.75 parts by mass or more and 29.75 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or more, relative to 100 parts by mass in total of the cured product of the curable resin compound and the specific cationic resin Parts by mass or less. When the content of one kind of the inorganic fine particles is too small, there is a tendency that the smooth touch feeling is insufficient. On the other hand, if the content of the inorganic fine particles is too large, there is a tendency that unpleasant tactile sensation which is distant from the smooth running smoothness tends to occur. In addition, the particles tend to fall off, and the smooth touch feeling is likely to change, making it difficult to sustain smooth running for a long period of time. Further, the surface decoration layer may become fragile, and the moldability may be deteriorated.

The content of the particles having the smallest average particle diameter out of the inorganic fine particles contained in the two or more kinds of inorganic fine particles is preferably 15 mass% or more and 85 mass% or less, more preferably 17 mass% or more and 75 mass% or less to be. The content of the particles having the largest average particle diameter out of the inorganic fine particles contained in two or more species is preferably 15 mass% or more and 85 mass% or less, more preferably 17 mass% or more and 75 mass% or less, Or less. If the particles having the smallest average particle diameter or the particles having the largest average particle diameter are too small, the smooth and smooth touch tends to be insufficient. On the other hand, when the particles having the smallest average particle diameter or the particles having the largest average particle diameter are too large, there is a tendency that unpleasant tactile sensations are produced which are remote from the smooth traveling carrier. In addition, the particles tend to fall off, and the smooth touch feeling is likely to change, making it difficult to sustain smooth running for a long period of time. Further, the surface decoration layer may become fragile, and the moldability may be deteriorated.

When an ionizing radiation curable resin compound is used as the curable resin compound, it is preferable to add a photopolymerization initiator to the coating liquid at the time of forming the surface decorating layer.

Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone , 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoyl formate, p- Carbonyl compounds such as hydroxyisobutylphenone,? -Hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenylketone; Sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone; Peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide, and the like. The photopolymerization initiator may be used alone or in combination of two or more. In addition, since the photopolymerization initiator is often useful, it is preferable that the ionizing radiation curable resin compound is not water-soluble.

The amount of the photopolymerization initiator to be added is not particularly limited, but is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the ionizing radiation curable resin compound. If the amount of the photopolymerization initiator is too small, it may take a long time to cure and the productivity may be lowered. If the photopolymerization initiator is too large, the surface decoration layer may be yellowed by the photopolymerization initiator.

When a thermosetting resin compound is used as the curing resin compound, it is preferable to add a crosslinking agent to the coating liquid at the time of forming the surface decorating layer.

Examples of the crosslinking agent include isocyanate crosslinking agents such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) Of these, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferable in that they are excellent in light resistance. Depending on the functional group of the thermosetting resin compound, an epoxy crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a melamine crosslinking agent, or the like may be used. The crosslinking agent may be one kind or two or more kinds.

The amount of the crosslinking agent added is not particularly limited, but is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the thermosetting resin compound. If the amount of the crosslinking agent is too small, the curing may take a long time and the productivity may be deteriorated. If the amount is too large, the resin may become hard and fragile.

A surfactant conventionally known as a leveling agent may be added to the coating liquid when forming the surface decorating layer in a range that does not impair the effect of the present invention. Thereby, the surface tension of the coating liquid can be lowered, and the appearance of the surface decorating layer, in particular dents due to minute bubbles, dents due to adherence of foreign matter, and cratering in the drying process can be improved. Further, in addition to the above-mentioned surfactants, known additives can be suitably contained in the coating liquid when forming the surface decorative layer.

The surface decorative layer may be prepared by adding the above-mentioned curable resin compound, inorganic fine particles, cationic resin, and various additives (photopolymerization initiator, crosslinking agent, leveling agent, etc.) , Coating the film on a base film, and drying and curing the film.

Examples of the organic solvent that can be used for the coating liquid when forming the surface decorative layer include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; Glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Ester solvents such as ethyl acetate and butyl acetate; And hydrocarbon solvents such as toluene and xylene. These organic solvents may be used alone or in combination of two or more.

Examples of the application method of the coating liquid when forming the surface decorating layer include a gravure coating method, a kiss coating method, a dipping method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, A gravure coating method which can be applied by a roll-to-roll coating method and is uniformly applied is preferable, and in particular, a reverse gravure coating method is preferable. desirable. The application amount of the coating liquid may be suitably set in accordance with the desired thickness of the surface decoration layer or the like.

The drying temperature after application of the coating liquid is not particularly limited. For example, it is preferably from 40 캜 to 130 캜, more preferably from 50 캜 to 80 캜. If the drying temperature is too low, there is a fear that the solvent remains in the coating film. If the drying temperature is too high, excessive formation of the coating film due to excessive heating (bubbling, cratering, etc.) may occur.

When an ionizing radiation curable resin compound is used as the curable resin compound, the irradiation amount of the active ray for curing the radiation curable resin compound is preferably 50 mJ / cm 2 to 1000 mJ / cm 2, more preferably 150 mJ / cm 2 to 700 mJ / to be. If the accumulated light quantity is too small, the polymerization reaction of the ionizing radiation curable resin compound is not promoted, and the surface hardness tends to remarkably decrease. When the integrated amount is too large, the base film may be deformed due to the effect of heat generated.

When a thermosetting resin compound is used as the curing resin compound, the heating temperature for curing the resin compound is preferably 40 占 폚 to 150 占 폚, more preferably 50 占 폚 to 100 占 폚. When the heating temperature at the time of curing is too low, the polymerization reaction of the thermosetting resin compound is not promoted and the surface hardness tends to remarkably decrease. When the heating temperature is too high, the base film may be deformed. The heating at the time of curing may also be performed after the application of the coating liquid as described above.

It is important that the surface decoration layer formed in the above-described manner has a surface roughness SMD of 0.4 탆 or more and 2.0 탆 or less as measured by a KES surface tester. Here, KES (Kawabata Evaluation System) is an objective evaluation method for feeling the feeling of clothes fabric established in the "Texture Measurement and Standardization Research Committee" established in the Japan Textile and Mechanics Institute. Surface roughness SMD is a method of evaluating the surface texture (scratching, Etc.). The smaller the value, the smaller the roughness, the roughness, the unevenness, the smoothness and the compactness. When the surface roughness SMD of the surface decorating layer is within the above range, it becomes appropriate denseness, so that a smooth running stock similar to the uncoated unmodified wood of the original can be expressed. The surface roughness SMD of the surface decoration layer is preferably 0.45 μm or more and 1.7 μm or less, and more preferably 0.55 μm or more and 1.4 μm or less. As an KES surface tester, an automated surface tester (KES-FB4) manufactured by Kato Tech Co., Ltd. can be used. The surface roughness SMD can be measured by, for example, a method described later in Examples.

The surface decor layer preferably has a static friction index of 1.0 to 4.5 as measured by a silicon sensor ruber with a KES surface friction tester. The static friction index is an index indicating whether or not the film is sticky, not sticking to the hand. When the static friction index of the surface decorating layer is within the above range, it is possible to more reliably suppress stickiness or a feeling of sticking to the hand, and furthermore, it is possible to impart a feeling of smoothness. The static friction index of the surface decorative layer is preferably 1.2 or more and 4.0 or less, and more preferably 1.3 or more and 3.7 or less. As the KES surface friction tester, a friction tester (KES-SE) manufactured by Kato Tech Co., Ltd. can be used. The measurement of the traction friction index can be performed, for example, by the method described later in the embodiment.

In order to allow the surface decorating layer to have the surface roughness SMD and the traction friction index in the above-mentioned range, for example, in addition to containing two or more kinds of inorganic fine particles satisfying the above-mentioned predetermined condition, the amount of the inorganic fine particles The total amount, the amount of each inorganic fine particle), the particle diameter of each inorganic fine particle, the particle diameter difference of each inorganic fine particle, and the like are all preferably controlled.

The thickness of the surface decoration layer is not particularly limited, but usually the lower limit is preferably 0.6 占 퐉, more preferably 1.0 占 퐉. The upper limit of the film thickness of the surface decoration layer is preferably 100 占 퐉, more preferably 80 占 퐉, further preferably 60 占 퐉, and particularly preferably 20 占 퐉. If the surface decoration layer is too thin, the inorganic fine particles are less likely to be retained on the surface decorating layer, so that the reduction of stickiness caused by the inorganic fine particles becomes insufficient and the smooth touch feeling may be damaged. On the other hand, if the surface decoration layer is too thick, the inorganic fine particles are completely embedded in the surface decoration layer, so that it is impossible to expect reduction of stickiness caused by the inorganic fine particles, and it becomes difficult to obtain smooth and smooth touch. In addition, there is a possibility that the curing resin compound is cured poorly and curling due to curing shrinkage may occur. The thickness of the surface decoration layer can be measured by, for example, a contact type film thickness meter.

(Substrate film)

The base film is not particularly limited, but a plastic film is preferable. Examples of the resin constituting the base film include polyester, polyolefin, polyamide, polyurethane, polyether, polystyrene, polyacrylic resin, polyvinyl resin and the like. Of these, polyester is particularly preferable.

The polyester preferably used as the constituent resin of the base film is, for example, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid or an ester thereof and a polyester such as ethylene glycol, diethylene glycol, 1,4-butanediol , Neopentyl glycol, and the like. The polycondensation between an aromatic dicarboxylic acid and a glycol may be carried out by a direct reaction method, a method in which an alkyl ester of an aromatic dicarboxylic acid is transesterified with a glycol and then subjected to polycondensation or a method in which a diglycol ester of an aromatic dicarboxylic acid is polymerized Or a method of adding the above-mentioned components to the solution. Representative examples of such polyesters include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate. These polyesters may be homopolymers or copolymers. In the case of the copolymer, the amount of the polyester unit such as ethylene terephthalate unit, butylene terephthalate unit and ethylene-2,6-naphthalate unit is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 80 mol% Is at least 90 mol%.

The base film may be an unstretched film, but it is preferably a stretched film from the viewpoint of the mechanical strength of the surface decorative film. The stretching may be uniaxial stretching or biaxial stretching, but a biaxially stretched film is preferable from the viewpoint of heat resistance and solvent resistance.

The thickness of the base film is not particularly limited, but is preferably 35 μm or more and 350 μm or less, more preferably 50 μm or more and 260 μm or less, and further preferably 75 μm or more and 200 μm or less. If the base film is too thick, the formability upon application to the decorative object may be deteriorated, and the intended use may be limited. In addition, the base film may be disadvantageous in terms of cost. When the base film is too thin, There is a tendency.

In the case of forming a printing layer which gives a shape or color to the surface of the base film opposite to the surface decoration layer as described later, the base film preferably has a total light transmittance of 80% or more. If the total light transmittance of the base film is too low, there is a possibility that the visibility of the printed layer seen from the side of the surface decoration layer becomes insufficient.

(Printing layer, adhesive layer, etc.)

The surface decorative film of the present invention may be provided with a print layer for imparting shape or color to the surface of the base film opposite to the surface decorative layer. Thereby, it is possible to provide excellent smooth transportability and decorate a desired appearance.

The printing method is not particularly limited, and various printing methods such as thermal transfer, heat transfer, sublimation transfer, intaglio printing, stencil printing, iron plate printing, flat printing, magnetic, electrostatic and ink jet printing can be applied.

The surface decorative film of the present invention may have an adhesive layer on the surface of the base film opposite to the surface decorative layer. In this case, the surface decorative film of the present invention can be adhered to the resin molded article to be decorated by the adhesive force of the adhesive layer.

The pressure-sensitive adhesive that can be used for forming the pressure-sensitive adhesive layer is not particularly limited and includes, for example, natural rubber, synthetic rubber, chloroprene rubber, NBR, butyl rubber, urethane rubber, vinyl acetate and copolymers thereof, acrylic acid and copolymers thereof Solvent type adhesive; Emulsion type adhesives such as natural rubber latex, chloroprene latex, NBR latex, vinyl acetate and its copolymer, acrylic acid and its copolymer; Water-soluble adhesives such as polyvinyl alcohol, starch, and glue; Thermosetting resins such as epoxy resin, polyester resin, urea and melamine resin, phenol resin and polyurethane resin; Paraffin wax, microcrystalline wax, asphalt, and resin wax mixture; Polyolefins such as polyethylene, and unsaturated polyesters. One kind of adhesive agent may be used, or two or more kinds thereof may be used.

When the surface decorative film of the present invention has the adhesive layer, it is preferable to form a release layer on the adhesive layer. Thereby, the adhesive force of the adhesive layer can be protected by the release layer during the time until the surface decoration film of the present invention is adhered to the resin molded article to be decorated, and the release layer can be easily peeled off at the time of attachment. The release layer may be formed, for example, by applying a known release agent.

This application claims the benefit of priority based on Japanese Patent Application No. 2013-014817 filed on January 29, 2013. The entire contents of the specification of Japanese Patent Application No. 2013-014817 filed on January 29, 2013 are incorporated herein by reference.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is of course not limited by the following Examples, and it is needless to say that the present invention is not limited thereto And are all included in the technical scope of the present invention.

In the following, "% " and " part " representing the content and amount of use are on a mass basis unless otherwise specified.

The methods for measuring the physical properties in the examples and comparative examples are as follows.

(Surface roughness SMD)

The thickness variation of the sample surface (surface decoration layer of the film) was measured using an automated surface tester (KES-FB4) manufactured by Kato Tech Co., Ltd. The measurement conditions were such that a load of 0.098 N was applied to a 0.5 mm diameter piano wire having a width of 5 mm and a friction distance of 30 mm, an analysis distance of 20 mm, and a sample moving speed of 1 mm / sec. The measurement was carried out under an environment of 20 deg. C and 65% RH, and the average value of five measurements was employed.

(Static friction index)

The surface friction coefficient was measured using a friction tester (KES-SE) manufactured by Kato Tech Co., Ltd. The measurement was carried out under the following conditions: a standard friction bar was used, and a silicone sensor (10 mm x 10 mm x 3 mm) made by Kato Tech Co., Ltd. was used as the rubbing member and a load of 0.245 N / cm 2 (25 gf / And the measurement sensitivity H (sensitivity 20 g / V). Other conditions such as friction distance and friction speed are as specified in the specification (friction distance 30mm, analysis distance 20mm, sample movement speed 1mm / sec). Then, a data logger (a multi-input data acquisition system manufactured by Keith Co.) was connected to the friction tester, the voltage value of the load obtained at the time of measurement was obtained, and the voltage value at the time when the friction started to move was used as the traction friction index. The measurement was carried out under an environment of 20 deg. C and 65% RH, and the average value of five measurements was employed. Further, it was confirmed in advance that a value of 3 or more was obtained when the static friction index was measured using a commercially available biaxially stretched polyester film ("Soft Shine (registered trademark)" by Toyobo Co., Ltd., thickness: 125 μm) as a sample Then, it was used for measurement.

(Average particle diameter)

Using a Coulter counter (Multisizer Type II, manufactured by Beckman Coulter, Inc.), the particles were dispersed in a non-swelling solvent to measure the volume average particle diameter.

[Example 1]

On a biaxially oriented polyester film (Softshine (registered trademark) TA009, thickness 125 占 퐉) containing a co-polyester having an easy adhesive layer on both sides, a coating liquid prepared by the following prescription was applied , And the coating layer was cured by using a wire bar so that the thickness of the coating layer after the coating and curing was 3 占 퐉 and dried for 60 seconds with hot air at 80 占 폚 and then hardened under a high pressure mercury lamp at an integrated light quantity (200 m) J / A film was obtained. Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Preparation of Coating Solution]

The following materials were mixed at the mass ratio shown below, and dissolved by stirring for 30 minutes or more. Subsequently, the undissolved product was removed using a filter having a nominal filtration accuracy of 100 탆 to prepare a coating liquid.

The average particle diameter and the content ratio of each of the inorganic fine particles contained in the coating liquid are as shown in Table 1 (the same applies to the following examples and comparative examples).

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 - Inorganic fine particles ("Siloid 74x4500" manufactured by GRACE Davison, average particle diameter 9.0 탆): 1.000 mass%

 - Inorganic fine particles ("Silo Jet P612", average particle diameter: 12.0 탆, manufactured by Grace DaVinci): 1.000 mass%

 (Photo-polymerization initiator (" Irgacure (registered trademark) 184 " manufactured by BASF Japan): 1.000 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

[Example 2]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 41.646 mass%

 Propylene glycol monomethyl ether: 27.764 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 18.509 mass%

 (Acet 1SX-1055, weight average molecular weight 40,000, solids content 40% by mass, manufactured by Taihe Fine Chemicals Co., Ltd.): 9.255 mass%

 - Inorganic fine particles ("Siloid 74x4500", average particle diameter 9.0 mu m, manufactured by Grace Dabi Co., Ltd.): 0.925 mass%

 · Inorganic fine particles ("Silo Jet P612", average particle diameter: 12.0 μm, manufactured by Grace DaVinci Co., Ltd.): 0.925 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 0.925 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Example 3]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.497 mass%

 Propylene glycol monomethyl ether: 28.998 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 18.509 mass%

 · Quaternary ammonium salt type cationic agent ("PAPIOGEN (registered trademark) P105", weight average molecular weight 20,000, solid content 60% by mass): 6.170 mass%

 - Inorganic fine particles ("Siloid 74x4500", average particle diameter 9.0 mu m, manufactured by Grace Dabi Co., Ltd.): 0.925 mass%

 · Inorganic fine particles ("Silo Jet P612", average particle diameter: 12.0 μm, manufactured by Grace DaVinci Co., Ltd.): 0.925 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 0.925 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Example 4]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 - Inorganic fine particles ("Siloid 72W", average particle diameter 3.0 μm, manufactured by Grace Dabi Co., Ltd.): 0.800 mass%

 - Inorganic fine particles ("Siloid 74x4500", average particle diameter 9.0 mu m, manufactured by Grace Dabi Co., Ltd.): 0.900 mass%

 · Inorganic fine particles ("Silo Jet P616", average particle diameter 16.0 μm, manufactured by Grace Dabi Co., Ltd.): 0.300 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Example 5]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 · Inorganic fine particles ("Siloid ED3", average particle diameter 5.0 μm) manufactured by Grace Dabi Co., Ltd.: 0.440 mass%

 · Inorganic fine particles ("Siloid 74x5500", average particle diameter 8.0 μm, manufactured by Grace Dabi Co., Ltd.): 0.958 mass%

 Inorganic fine particles ("Siloid 74x4500", average particle diameter 9.0 mu m, 10% PGM dispersion, manufactured by Grace DaVinci Co., Ltd.): 0.240 mass%

 - Inorganic fine particles ("Silo Jet P612", average particle diameter: 12.0 탆, 10% PGM dispersion, manufactured by Grace Dabi Co., Ltd.): 0.360 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Example 6]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 · Inorganic fine particles ("Siloid W300", average particle size 5.0 μm) manufactured by Grace Dabi Co., Ltd.: 0.667 mass%

 - Inorganic fine particles ("Silyloid W500", average particle diameter 8.0 μm) manufactured by Grace Dabi Co., Ltd.: 0.667 mass%

 · Inorganic fine particles ("Siloid W900", average particle diameter 13.0 μm, manufactured by Grace Dabi Co., Ltd.): 0.667 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Example 7]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 - Inorganic fine particles ("Siloid 74x5500", average particle diameter 8.0 μm) manufactured by Grace Dabi Co., Ltd.: 1.000 mass%

 - Inorganic fine particles ("Siloid 74x6500", average particle diameter 6.0 mu m, manufactured by Grace Dabi Co., Ltd.): 0.500 mass%

 · Inorganic fine particles ("Silyloid ED2", average particle diameter 4.0 μm) manufactured by Grace DaVinci Co., Ltd.: 0.500 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Example 8]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 · Inorganic fine particles ("Silo Jet P616", average particle diameter 16.0 μm, manufactured by Grace Dabi Co., Ltd.): 0.900 mass%

 - Inorganic fine particles ("sicastar", average particle diameter 50.0 μm, manufactured by Coron Front): 0.300 mass%

 - Inorganic fine particles (" Shikastar ", manufactured by Core Front, average particle diameter 20.0 占 퐉): 0.800 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Comparative Example 1]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 41.297 mass%

 Propylene glycol monomethyl ether: 27.531 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 14.364 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271" manufactured by Arakawa Chemical Industries, Ltd., bifunctional, 100% by mass of solid content): 9.576 mass%

 (Acet 1SX-1055, weight average molecular weight 40,000, solids content 40% by mass, manufactured by Taihe Fine Chemicals Co., Ltd.): 5.985 mass%

 Light polymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.197 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Comparative Example 2]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 - Inorganic fine particles ("Siloid 74x4500", average particle size 9.0 탆, manufactured by Grace Dabi Co., Ltd.): 1.999 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Comparative Example 3]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 - Inorganic fine particles ("Siloid 74x4500", average particle diameter 9.0 mu m, manufactured by Grace Dabi Co., Ltd.): 1.000 mass%

 - Inorganic fine particles (" P409 ", average particle diameter 9 mu m, manufactured by Grace DaVinci Co., Ltd.): 1.000 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Comparative Example 4]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 - Inorganic fine particles (" P616 ", average particle diameter 16 mu m, manufactured by Grace DaVinci Co., Ltd.): 1.000 mass%

 Organic fine particles ("Turpent (registered trademark) YK-30", average particle diameter 33 μm, manufactured by Toyo Bosch Co., Ltd.): 1.000 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Comparative Example 5]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 43.178 mass%

 Propylene glycol monomethyl ether: 28.786 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 11.994%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 7.996%

 (Acet 1SX-1055, manufactured by Taihe Fine Chemical Co., Ltd., weight average molecular weight: 40,000, solid content: 40% by mass): 4.998 mass%

 Organic fine particles (Turfic (registered trademark) YK-80, average particle diameter 80 mu m, manufactured by Toyobo Co., Ltd.): 1.999 mass%

Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 Silicone surfactant (DC57 made by Toray Dow Corning): 0.050 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Comparative Example 6]

A surface decorative film was obtained in the same manner as in Example 1, except that the formulation of the coating liquid in Example 1 was changed as follows.

 Methyl ethyl ketone: 42.000 mass%

 Propylene glycol monomethyl ether: 27.750 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 577", 3 to 6 functionalities, solid content 100% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.): 11,000 mass%

 Urethane acrylate UV / EB curing resin ("Beam Set (registered trademark) 271", bifunctional, solid content 100% by mass, manufactured by Arakawa Chemical Industries, Ltd.): 7.000%

 (Acet 1SX-1055, weight average molecular weight 40,000, solids content 40% by mass, manufactured by Taihe Fine Chemicals Co., Ltd.): 3.200 mass%

 - Inorganic fine particles ("Siloid 74x4500", average particle diameter 9.0 mu m, manufactured by Grace Dabi Co., Ltd.): 4.000 mass%

 · Inorganic fine particles ("Silo Jet P612", average particle diameter 12.0 μm, manufactured by Grace Dabi Co., Ltd.): 4.000 mass%

 Photopolymerization initiator ("Irgacure (registered trademark) 184" manufactured by BASF Japan Ltd.): 1.000 mass%

 · Silicon surfactant ("DC57" manufactured by Dow Corning Toray Co., Ltd.): 0.05 mass%

Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Referential Example 1]

(Trade name: SUMITEX (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.) was applied on the corona discharge treated surface side of a polyester film containing a fine void therein ("Crisper (registered trademark) G1211" (Dry) was mixed with 89 parts by mass of water and 1 part by mass of a catalyst (Sumitex (registered trademark) ACX manufactured by Sumitomo Chemical Co., Ltd.) in an amount of 10 parts by mass , And dried. (GH-20, manufactured by Nippon Kogei Kagaku Co., Ltd.), melamine resin (Sumitex (registered trademark) M-3 made by Sumitomo Chemical Co., Ltd.) as a curing agent, a cationic substance , Silica particles having an average particle diameter of 5 占 퐉 ("Silo Jet P405" manufactured by Grace Dabi Co., Ltd.) and silica particles having an average particle diameter of 12 占 퐉 (Grace DaVision Co., (Silo Jet P412 manufactured by Mitsubishi Chemical Corporation) was adjusted to 10/1/2 // 10/10 (mass ratio) as a final solids content by a 10% aqueous solution, wire bar coating and heat treatment for 4 minutes in a gear oven at 140 deg. Followed by curing and drying. The coating amount was adjusted to 12 g / m < 2 > to obtain a surface decorative film. Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Reference Example 2]

10 parts by mass of a melamine resin ("Sumitex (registered trademark) M-3" manufactured by Sumitomo Chemical Co., Ltd.) was coated on the corona discharge treated surface side of a polyester film (Crisper (registered trademark) G1211 thickness, And 1 part by mass of a catalyst (Sumitex (registered trademark) ACX manufactured by Sumitomo Chemical Co., Ltd.) were mixed in 89 parts by mass of water to give a coating liquid of 0.1 g / m 2 (at the time of drying), followed by drying. (RS117 available from Kuraray Co., Ltd.) as a water-soluble resin, dimethylol hydroxyethylene urea resin (SR5004 available from Sumitomo Chemical Co., Ltd.) as a curing agent, a cationic resin (Nippon Kaya Co., Silica particles having an average particle diameter of 5 占 퐉 ("Silo Jet P405" manufactured by Grace Dabi Co., Ltd.) and silica particles having an average particle diameter of 12 占 퐉 ("Silo Jet P412" ) Was adjusted to 10/3/1 // 10/10 (mass ratio) as the final solid content, and the wire was immediately coated and heated at a hot air speed of 15 m / min at 100 ° C./120 ° C./140 ° C. / 120 占 폚, for 30 seconds in total, for 2 minutes, followed by drying and curing. The coating amount was adjusted to 14 g / m < 2 > to obtain a surface decorative film. Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Referential Example 3]

In the same manner as in Reference Example 2 except that a polyester film ("Crisper (registered trademark) G1211" thickness, 100 μm, manufactured by Toyobo Co., Ltd.) was used and a water-soluble resin, a curing agent, a cationic material, A surface decorating film was obtained in the same manner as in Reference Example 2 except that the particles and the silica particles having an average particle diameter of 12 占 퐉 were used so as to have a final solid content of 10/1/2/10/10 (mass ratio), respectively. Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

[Reference Example 4]

In Reference Example 2, a polypropylene film ("Pearl Film Pyrene (registered trademark) P6255", thickness 120 占 퐉) containing fine voids therein was used instead of the polyester film containing fine voids therein , A water-soluble resin, a curing agent, a cationic material, silica particles having an average particle diameter of 5 탆 and silica particles having an average particle diameter of 12 탆 were used so as to have a final solid content of 10/1/1 // 10/10 (mass ratio) A surface decorative film was obtained in the same manner as in Reference Example 2 except that the drying temperature was set in the order of 80 占 폚 / 100 占 폚 / 120 占 폚 / 100 占 폚. Various physical properties (initial surface roughness (SMD) and traction friction index of the surface decorating layer) of the obtained surface decorating film were as shown in Table 2.

The surface decorative films obtained in the above Examples and Comparative Examples were evaluated as follows. The results are shown in Table 2.

(Initial tactile evaluation)

We collected five healthy men and five men (10 in total) as subjects from 10 to 40 years old. Each of the subjects was placed in a constant temperature and humidity chamber humidified at 26 ° C and 60% RH, and allowed to stand for about 30 minutes. Thereafter, an A4 sized surface decorative film was applied to a white paper ("Echo400 ECO4100" (Surface of the surface decorating layer) was freely touched by the fingertip or the palm of the hand, and the touch of the surface was questioned. The question items are four items of "smoothness", "compactness", "no feeling of sticking to the hand" and "feeling of touch of the wood" felt when putting a hand on the film surface , And the judgment was made in four stages of "⊚", "◯", "Δ" and "×" based on the following judgment criteria. The result of the judgment that the number of the answerers was the greatest among the subjects was regarded as the result of each sample. All of the initial tactile evaluations were carried out after storing the produced surface decorative film for 10 days in a normal state (room temperature).

"Smooth"; ◎: It feels very smooth.

                ○: It feels smooth.

                ?: Some feeling of smooth running is felt.

                X: No smoothness is felt.

 "Compactness"; ◎: The texture feels satisfactory.

             ○: Texture is felt.

             ?: The texture is slightly felt.

             X: The texture is not felt.

"There is no feeling of sticking to the hand"; ◎: The feeling of sticking to the hand is not felt at all.

                              ○: There is no feeling of sticking to the hand.

                              △: The feeling of sticking to the hand is felt a little.

                              X: The feeling of sticking to the hand is felt.

"Can you feel the touch of wood"; ◎: Feeling of wood is felt very much.

                              ○: The feel of the wood is felt.

                              △: Feeling of the wood feeling is slightly felt.

                              X: The feel of the wood is not felt.

(Change over time)

The obtained surface decorative film was subjected to the following weathering test and then the surface roughness (SMD) and the traction friction index of the surface decorating layer were measured again and the initial surface roughness (SMD) or the surface roughness after the weather test SMD) or the value obtained by subtracting the traction friction index (change value), and at the same time, the surface decorative film after the weather test was evaluated as "smooth running" by the same method as the initial tactile evaluation described above. The variation of the surface roughness (SMD) is within the tolerance range of ± 0.1, and the variation range of the static friction index is within the tolerance range of ± 0.4.

[Weather test]

The test was carried out using a WEL-SUN-HCH B type sunshine super long life weigh meter (manufactured by Suga Shikai Co., Ltd.) according to JIS K 5400 (accelerated weathering resistance) for 18 minutes in an irradiation temperature of 63 캜, a humidity of 50% RH, The surface decorative film as a sample was irradiated for 200 hours under the condition of rain. After the irradiation, the sample was air-dried for 5 hours or more in an atmosphere of 23 ° C and 50% RH.

From Table 2, it can be seen that the surface decorative film of the present invention obtained in the examples exhibits sufficient smooth running feel at the beginning of decoration and makes the feel of the wood feel. However, the surface decorative film obtained in each Comparative Example is insufficient in smooth- It can be understood that the feel of the wood is not felt. Further, the surface decorative film of the present invention obtained in each Example is small in change with time, and can be continuously conveyed for a long period of time. However, the surface decorative film obtained in each Reference Example has a large change with time, It can be seen that it is difficult to sustain the shipment for a long period of time.

The surface decorative film of the present invention is useful for, for example, a construction material application, a built-in application of a vehicle or a furniture, and various molding processing applications in which a surface decoration is performed by using a film. Especially, For example, a housing or member of a mobile personal computer, an OA appliance or a home appliance, an automobile interior member such as an instrument panel or a handle).

Claims (8)

A surface decorative film having a surface decorative layer on a base film,
Wherein the surface decoration layer comprises a cured product of a curable resin compound and a cationic resin of a quaternary ammonium salt type having a weight average molecular weight of 20,000 to 100,000 and at least two kinds of inorganic fine particles satisfying the following conditions (i) to (iv) And the surface decoration layer has a surface roughness SMD of 0.40 탆 to 2.0 탆 measured by a KES surface tester.
(i) those having an average particle diameter in the range of 1.0 to 50 mu m
(ii) those having an average particle diameter different by 1.0 占 퐉 or more
(iii) the average particle diameter of the particles having the smallest average particle diameter is 1.0 μm or more and 16 μm or less
(iv) the average particle diameter of the particles having the largest average particle diameter is not less than 8 μm and not more than 50 μm The surface decorative film according to claim 1, wherein the surface decorating layer has a static friction index of 1.0 to 4.5, which is measured using a silicon sensor ruber with a KES surface friction tester. The surface decorative film according to claim 1 or 2, wherein the total content of the inorganic fine particles is 5 to 35 parts by mass based on 100 parts by mass in total of the cured product of the curable resin compound and the cationic resin. 4. The surface-treated decorative composition according to any one of claims 1 to 3, wherein the content of the particles having the smallest average particle diameter among the inorganic fine particles contained in the two or more kinds of inorganic fine particles is 15% by mass or more and 85% film. The surface finishing method according to any one of claims 1 to 4, wherein the content of the particles having the largest average particle diameter among the inorganic fine particles contained in two or more species is 15 mass% or more and 85 mass% or less with respect to the total inorganic fine particles film. The surface-decorated film according to any one of claims 1 to 5, wherein the content of the inorganic fine particles is 0.75 to 29.75 parts by mass based on 100 parts by mass of the sum of the cured product of the curable resin compound and the cationic resin . The surface decorative film according to any one of claims 1 to 6, wherein the quaternary ammonium salt type cationic resin is contained in an amount of 2 to 25 parts by mass based on 100 parts by mass of the cured resin composition. The surface decorative film according to any one of claims 1 to 7, wherein the curable resin compound comprises 5% by mass or more of an ionizing radiation curable resin compound having three or more functions.