KR102180699B1 - Film for surface decoration - Google Patents

Abstract

An object of the present invention is to provide a film for surface decoration capable of expressing sufficient softness at the beginning of decoration and maintaining sufficient softness even over a long period of time. The surface decoration film of the present invention is a surface decoration film having a surface decoration layer on a base film, wherein the surface decoration layer is a cured product of a curable resin compound, and a quaternary ammonium salt type having a weight average molecular weight of 20,000 to 100,000 Cation-based resin and two or more inorganic fine particles satisfying a predetermined condition for an average particle diameter, and the surface decoration layer has a surface roughness SMD of 0.40 µm or more and 2.0 µm as measured by a KES surface tester It is characterized by the following, and is excellent in softness.

Description

Surface decoration film {FILM FOR SURFACE DECORATION}

The present invention relates to a film for surface decoration capable of imparting a soft touch.

BACKGROUND ART Conventionally, the surface of various resin molded bodies such as automobile interior parts, electric product housings, and building materials has been decorated using a film, and various decorative films are known. However, most of them are to improve the appearance (so-called appearance) by imparting gloss, color, pattern, and the like, and hardly any decorative film for the purpose of imparting a desired touch to the surface of a resin molded body has been reported.

By the way, even if you give the resin molded body a desired (for example, imitation of solid wood), the touch felt when actually touched is the touch that is imagined from the exterior (for example, if it is imitating solid wood, it is soft. If it is far from the one touch), it does not fit the consumer's genuine intention, and the product value cannot be sufficiently increased.

When the product value is increased by imparting touch to the resin molded body, the touch required for the resin molded body varies depending on its appearance and the like. For example, if the exterior has a grain pattern imitating solid wood, a soft touch similar to that of genuine solid wood (in this specification, it may be referred to as ``soft'') is desired, and if the exterior imitates leather , A moist touch similar to genuine leather is required. Among the various touches, the present inventors first proposed a decorative film capable of imparting the touch of white wood to the surface of the resin molded body, focusing on "softness" (Patent Document 1). Specifically, a surface decoration layer composed of a water-soluble resin (A), a curing agent (B), a cationic substance (C), and a particle (D) in a predetermined ratio is provided on the base film surface, and the surface decoration It is a decorative film in which the coating amount and bulk density of the layer are controlled in a specific range. This decorative film is intended to exhibit "smoothness" by absorbing moisture on the surface of the molded body by the hygroscopicity of the water-soluble resin itself, and by containing a large amount of particles to make the surface decorative layer a porous structure.

Japanese Patent Publication No. 2012-218284

However, when the surface of the resin molded body is decorated using the surface decoration film described in Patent Document 1, a sufficient softness is obtained at the beginning of the decoration, but if this molded body is used for a long period of time, the softness that was initially felt will be over time. There was a case of decline. Although the cause is not clear, there is a limit to the hygroscopicity that can be expressed by the water-soluble resin, and it is speculated whether it is due to the fact that moisture absorbed by the water-soluble resin is difficult to moisture-proof.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a surface decoration film capable of expressing sufficient softness at the beginning of decoration and maintaining sufficient softness even over a long period of time.

In addition, the term ``softness'' as used herein refers to a feeling that is expressed by having no stickiness as if sticking to the hand, and having a moderate density, and is made of solid wood (in detail, painted with paint or varnish, etc.). It is nice to the touch of a solid wood).

In order to solve the above problems, the inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, two or more types of inorganic fine particles that are difficult to feel sticky, and a cationic resin having an average molecular weight in a specific range, together with a cured resin material, are used as a surface decorative layer. At the same time, two or more types of inorganic fine particles satisfying a predetermined condition are selected, and the surface roughness SMD measured by the KES surface tester is controlled within a predetermined range capable of reproducing the appropriate density. By doing this, it was found that the initial softness of the decoration can be increased and the durability thereof can be improved, and the present invention was completed.

That is, the present invention includes the following configurations.

(1) A surface decoration film having a surface decoration layer on a base film, wherein the surface decoration layer is 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 , Containing two or more kinds of inorganic fine particles satisfying the following conditions (i) to (iv), and the surface decoration layer is characterized in that the surface roughness SMD measured by the KES surface tester is 0.40 μm or more and 2.0 μm or less. A film for surface decoration with excellent softness.

(i) the average particle diameter is in the range of 1.0 to 50㎛

(ii) The average particle diameter is different from each other by 1.0 μm or more

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

(iv) The average particle diameter of the particles with the largest average particle diameter is 8 µm or more and 50 µm or less.

(2) The film for surface decoration according to the above (1), wherein the surface decoration layer has a static friction index of 1.0 to 4.5 measured using a silicon sensor friction ruler with a KES surface friction tester.

(3) The film for surface decoration according to (1) or (2), wherein the total content of the inorganic fine particles is 5 to 35 parts by mass with respect to 100 parts by mass of the cured product of the curable resin compound and the cationic resin in total.

(4) According to any one of the above (1) to (3), wherein the content of the particles with the smallest average particle diameter of the inorganic fine particles contained in two or more types relative to the total inorganic fine particles is 15% by mass or more and 85% by mass or less. Described surface decorative film.

(5) Of the inorganic fine particles contained in two or more types, the content of the particles having the largest average particle diameter with respect to the total inorganic fine particles is 15% by mass or more and 85% by mass or less, in any one of the above (1) to (4). Described surface decorative film.

(6) The content per one kind of inorganic fine particles is 0.75 to 29.75 parts by mass per 100 parts by mass of the cured product of the curable resin compound and the cationic resin in total, according to any one of (1) to (5) above. Film for surface decoration.

(7) For surface decoration according to any one of (1) to (6), comprising 2 to 25 parts by mass of the cationic resin of the quaternary ammonium salt type based on 100 parts by mass of the cured product of the curable resin compound. film.

(8) The film for surface decoration according to any one of (1) to (7), wherein the curable resin compound contains 5% by mass or more of a trifunctional or higher ionizing radiation curable resin compound.

According to the film for surface decoration of the present invention, it becomes possible to express sufficient softness at the beginning of decoration and to maintain sufficient softness even over a long period of time.

Since the softness expressed by the surface decorative film of the present invention is the same as unpainted solid wood, for example, if decoration such as printing of a grain pattern is performed on the exterior, it is more approximate to genuine solid wood. It becomes a molded product and can increase product value. In addition, since the softness expressed by the film for surface decoration of the present invention lasts for a long period of time, this product value is further increased.

The film for surface decoration of the present invention is useful, for example, for use in building materials, interior applications such as vehicles and furniture, and for various molding applications in which surface decoration is performed using a film, and in particular, items that are frequently touched (cell phones, It is suitably used as a film for surface decoration for a mobile personal computer, a housing or member of an OA device or home appliance, an automobile interior member such as an instrument panel or a steering wheel, etc.).

The film for surface decoration of the present invention is a decorative film having a surface decoration layer on at least one side of the base film, and providing a soft touch to the surface of the object to be decorated (such as a resin molded body), and is excellent in softness.

(Surface decoration layer)

The surface decoration layer in the present invention contains a cured product of a curable resin compound, a cationic resin, and two or more types of inorganic fine particles, for example, a curable resin compound, a cationic resin, and two or more types of inorganic fine particles. It is formed by applying a coating liquid containing a 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 an active ray (ultraviolet, radiation, electron beam, etc.) It is broadly classified into an ionizing radiation curable resin compound cured by irradiation and a thermosetting resin compound cured by heat, preferably an ionizing radiation curable resin compound. The surface decoration layer is constituted of a cured product obtained by imparting necessary external excitation energy to a curable resin compound formed in a thin film shape (layer shape) and cured.

Examples of the ionizing radiation curable resin compound include (meth)acrylate resins such as ultraviolet curable urethane (meth)acrylate resin, ultraviolet curable polyester (meth)acrylate resin, ultraviolet curable epoxy (meth)acrylate resin, or raw material compounds thereof. ) An acrylate-based ionizing radiation-curable resin compound is mentioned. Among these, an ultraviolet curable urethane acrylate resin is preferable.

As said ionizing radiation-curable resin compound, it is preferable to contain a trifunctional or more ionizing radiation-curable resin compound, and it is preferable to use a bifunctional ionizing radiation-curable resin compound together as needed. Thereby, the surface decoration layer can be made into what has suitable hardness and flexibility. In this case, the trifunctional or higher ionizing radiation-curable resin compound is preferably 5% by mass or more, and more preferably 10% by mass or more in the curable resin compound. The upper limit is not particularly limited, but preferably 95% by mass or less is good.

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

(a) (meth)acrylic acid diesters of alkylene glycol having 2 to 12 carbon atoms: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.,

(b) (meth)acrylate acid diesters of polyoxyalkylene glycol: diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, di Propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc.,

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

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

(e) Two (meth)acryloyl oxides in the molecule obtained by further reacting a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance with an alcoholic hydroxyl group-containing (meth)acrylate Urethane (meth)acrylates having a period,

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

When a (meth)acrylate-based ionizing radiation-curable resin compound is used as the ionizing radiation-curable resin compound, as a trifunctional or higher (meth)acrylate-based ionizing radiation-curable resin compound, specifically,

(a) Pentaerythritol tri(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, etc.,

(b) Three or more (meth)acrylics in a molecule obtained by further reacting a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound with two or more alcoholic hydroxyl group-containing compounds in advance, and an alcoholic hydroxyl group-containing (meth)acrylate. Urethane (meth)acrylates having a monooxy group,

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

As a thermosetting resin compound, a thermosetting urethane resin, thermosetting acrylic resin, thermosetting silicone resin, thermosetting polyester resin, thermosetting vinyl ester resin, thermosetting epoxy resin, thermosetting phenol resin, etc. are mentioned, for example. Among these, a thermosetting urethane resin is particularly preferred.

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

The cationic resin contained in the surface decoration layer of the present invention is a quaternary ammonium salt type cationic resin (hereinafter also referred to as "specific cationic resin") having a weight average molecular weight of 20,000 to 100,000. By containing a specific cationic resin having a molecular weight in this specific range, the surface decoration layer exhibits high hydrophilicity, so it is easy to absorb moisture from the palm that touches the surface decoration layer, and it helps to express a soft touch. At the same time, it becomes possible to sustain the soft touch over a long period of time.

As a quaternary ammonium salt type cationic resin that becomes a specific cationic resin, for example, dimethylaminoalkylmethacrylate (for example, dimethylaminoethylmethacrylate, etc.) or dimethylaminoalkylacrylamide (for example, A resin obtained by copolymerizing a monomer such as an alkyl halide salt of dimethylaminopropylacrylamide (for example, a methyl chloride salt) with a monomer of a (meth)acrylic acid ester (preferably a methacrylic ester). . As a commercial item, cationic agents, such as the Acrit series manufactured by Taisei Fine Chemicals, the Papiogen (registered trademark) series, and the Unisense series manufactured by Senka Corporation, are mentioned, for example.

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, even more 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 2 parts by mass or more and 25 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 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 becomes difficult to sustain the softness over a long period of time, and if it is too large, the surface strength may decrease or abnormal appearance may occur due to bleed out of the cationic resin.

The inorganic fine particles contained in the surface decoration layer of the present invention mainly impart a stickiness difficulty to the surface decoration layer, and help to realize a soft feel. And by selecting and containing two or more types having an average particle diameter that satisfies a predetermined condition as inorganic fine particles, it becomes possible to sustain the softness over a long period of time.

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

(i) the average particle diameter is in the range of 1.0 to 50 µm (preferably in the range of 3.0 to 30 µm, more preferably in the range of 6.0 to 15 µm)

(ii) those having an average particle diameter different from each other by 1.0 µm or more (preferably 2.0 µm or more, more preferably 3.0 µm or more)

(iii) The average particle diameter of the particles with the smallest average particle diameter is 1.0 μm or more and 16 μm or less (preferably 3.0 μm or more and 15 μm or less, more preferably 6.0 μm or more and 13 μm or less).

(iv) The average particle diameter of the particles with the largest average particle diameter is 8 µm or more and 50 µm or less (preferably 10 µm or more and 30 µm or less, more preferably 12 µm or more and 20 µm or less).

In addition, the average particle diameter of the inorganic fine particles in the present invention means a volume average particle diameter measured by a Coulter counter method.

In the present invention, when attempting to obtain the average particle diameter of two or more inorganic fine particles at the same time, the average particle diameter of each particle is obtained by separating the detected peaks. In this case, considering the ease of peak separation, the above (ii) The larger the difference in average particle diameter, which is a requirement, is more preferable, and particularly preferably 3.0 µm or more.

The type of inorganic fine particles is not particularly limited, and examples include titanium dioxide, calcium carbonate, silicon dioxide (silica), barium sulfate, aluminum oxide, aluminum hydroxide, zeolite, zinc oxide, talc, and benzoguanamine particles. Among these, silicon dioxide and talc are preferable. In addition, the shape of the inorganic fine particles is not particularly limited, and all shapes such as spherical, flat plate, rod shape, irregular shape, and those with different aspect ratios can be employed, but from the viewpoint of being easy to realize a soft touch, irregular particles are desirable.

Further, in the present invention, at least two or more types of inorganic fine particles having different average particle diameters may be used, and the types and shapes of the two or more types of inorganic fine particles may be the same or different, respectively.

The total content of the inorganic fine particles is preferably 5 parts by mass or more and 35 parts by mass or less, more preferably 5.5 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the total of the cured product of the curable resin compound and the specific cationic resin. Parts by mass or less, more preferably 6 parts by mass or more and 25 parts by mass or less. If the total content of the inorganic fine particles is too small, there is a tendency that the soft touch becomes insufficient. On the other hand, when the total content of the inorganic fine particles is too large, there is a tendency to become a rough and unpleasant touch that is far from smooth. In addition, the particles tend to fall off, the soft touch tends to change, and it may be difficult to sustain the softness for a long time. In addition, there is a fear that the surface decoration layer becomes brittle and the moldability is 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 with respect to 100 parts by mass of the total of the cured product of the curable resin compound and the specific cationic resin. It is not more than parts by mass. If the content per one kind of inorganic fine particles is too small, there is a tendency that the soft touch tends to be insufficient. On the other hand, when the content per one kind of inorganic fine particles is too large, there is a tendency for a rough and unpleasant touch that is far from smooth. In addition, the particles tend to fall off, the soft touch tends to change, and it may be difficult to sustain the softness for a long time. In addition, there is a fear that the surface decoration layer becomes brittle and the moldability is deteriorated.

Of the inorganic fine particles contained in two or more types, the content of the particles having the smallest average particle diameter relative to the total inorganic fine particles is preferably 15% by mass or more and 85% by mass or less, and more preferably 17% by mass or more and 75% by mass or less. to be. Further, of the inorganic fine particles contained in two or more types, the content of the particles having the largest average particle diameter with respect to the total inorganic fine particles is preferably 15% by mass or more and 85% by mass or less, and more preferably 17% by mass or more and 75% by mass. Below. When there are too few particles with the smallest average particle diameter or particles with the largest average particle diameter, the soft touch tends to be insufficient. On the other hand, when there are too many particles with the smallest average particle diameter or particles with the largest average particle diameter, there is a tendency for a rough and unpleasant touch that is far from smooth. In addition, the particles tend to fall off, the soft touch tends to change, and it may be difficult to sustain the softness for a long time. In addition, there is a fear that the surface decoration layer becomes brittle and the moldability is 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 when forming the surface decoration layer.

As a photoinitiator, for example, 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, methylbenzoyl formate, p-isopropyl-α- Carbonyl compounds such as hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenylketone; Sulfur compounds such as tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, thioxanthone, 2-chloro thioxanthone, and 2-methyl thioxanthone; Peroxide compounds, such as benzoyl peroxide and di-t-butyl peroxide, etc. are mentioned. A photoinitiator may be used alone or in combination of two or more. In addition, since many photoinitiators are oil-soluble, from this point, it is preferable that the ionizing radiation-curable resin compound is not water-soluble.

Although the amount of the photoinitiator added is not particularly limited, for example, 0.01 parts by mass or more and 15 parts by mass or less are preferable, and 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 photopolymerization initiator is too small, it may take a long time for curing and the productivity may decrease, and if too large, the surface decorative layer may be yellowed by the photopolymerization initiator.

When a thermosetting resin compound is used as the curable resin compound, it is preferable to add a crosslinking agent to the coating liquid when forming the surface decoration layer.

Examples of the crosslinking agent include isocyanate-based crosslinking agents such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). These Among them, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferable from the viewpoint of excellent light resistance. Further, 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. Only 1 type may be sufficient as a crosslinking agent, and 2 or more types may be sufficient as it.

Although the amount of the crosslinking agent added is not particularly limited, for example, 0.1 parts by mass or more and 30 parts by mass or less are preferable, and 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 crosslinking agent is too small, it may take time to cure and productivity may decrease, and if too much, the resin may become hard and brittle.

In the coating liquid for forming the surface decoration layer, a conventionally known surfactant as a leveling agent can be further contained within a range not impairing the effects of the present invention. Thereby, the surface tension of the coating liquid can be lowered, and the appearance of the surface decoration layer, particularly, dropout due to microbubbles, dents due to adhesion of foreign matters, etc., can be improved, such as cratering in the drying step. In addition, in addition to the above-described surfactant, known additives can be suitably contained in the coating liquid for forming the surface decoration layer.

For the surface decoration layer, for example, the above-described curable resin compound, inorganic fine particles, cationic resin, and various additives (photoinitiator, crosslinking agent, leveling agent, etc.) to be contained as needed are added to a suitable organic solvent to prepare a coating solution. , It can be formed by applying this on a base film and performing drying and curing treatment.

Examples of the organic solvent that can be used in the coating liquid for forming the surface decoration 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; Hydrocarbon solvents, such as toluene and xylene, etc. are mentioned. These organic solvents can be used alone or in combination of two or more.

As a method of applying the coating liquid when forming the surface decoration layer, gravure coating method, kiss coating method, dipping method, spray coating method, curtain coating method, air knife coating method, blade coating method, reverse roll coating method, bar coating A known coating method such as a method or a lip coating method can be employed, and among them, a gravure coating method that can be applied by a roll-to-roll method and can be uniformly applied is preferable. In particular, a reverse gravure method is used. desirable. The application amount of the coating liquid may be appropriately set according to the film thickness of the desired surface decoration layer.

The drying temperature after applying the coating liquid is not particularly limited, but is preferably 40°C or more and 130°C or less, and more preferably 50°C or more and 80°C or less. If the drying temperature is too low, there is a possibility that the solvent will remain in the coating film, and if it is too high, abnormality (bubble generation, cratering, etc.) may occur in the formed coating film due to excessive heating, resulting in a poor appearance.

When an ionizing radiation-curable resin compound is used as the curable resin compound, the amount of actinic radiation to cure it is preferably 50 mJ/cm 2 or more and 1000 mJ/cm 2 or less, more preferably 150 mJ/cm 2 or more and 700 mJ/cm 2 or less as the accumulated light amount. to be. When the amount of accumulated light is too small, the polymerization reaction of the ionizing radiation-curable resin compound is not accelerated, and the surface hardness tends to decrease remarkably. When the amount of accumulated light is too large, the base film may be deformed under the influence of the generated heat.

When a thermosetting resin compound is used as the curable resin compound, the heating temperature for curing it is preferably 40°C or more and 150°C or less, and more preferably 50°C or more and 100°C or less. If the heating temperature at the time of curing is too low, the polymerization reaction of the thermosetting resin compound is not accelerated, and the surface hardness tends to decrease remarkably, and if it is too high, the base film may be deformed. In addition, heating during curing may also serve as drying after applying the above-described coating liquid.

It is important that the surface decoration layer formed as described above has a surface roughness SMD of 0.4 µm or more and 2.0 µm or less as measured by a KES surface tester. Here, KES (Kawabata Evaluation System) is an objective evaluation method of the texture of clothing fabrics established by the 「Texture Measurement and Standardization Research Committee」 established in the Japanese Textile Machinery Society, and the surface roughness SMD is the surface texture (roughness, roughness, irregularity). Etc.), and a smaller value means less roughness, no roughness, no irregularities, and smoother and more detailed. When the surface roughness SMD of the surface decoration layer is within the above range, it becomes appropriately dense, and smoothness such as a genuine unpainted wood 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. In addition, as the KES surface tester, an automated surface tester (KES-FB4) manufactured by Katotech Co., Ltd. can be used, and the surface roughness SMD can be measured, for example, by a method described later in Examples.

It is preferable that the surface decoration layer has a static friction index of 1.0 to 4.5 measured using a silicon sensor friction ruler with a KES surface friction tester. The static friction index is an index indicating whether the film is not sticky and does not stick to the hand. When the static friction index of the surface decorative layer is within the above range, stickiness or sticking to the hand sensation can be suppressed more reliably, and further, a softer touch can be provided. The static friction index of the surface decoration layer is preferably 1.2 or more and 4.0 or less, and more preferably 1.3 or more and 3.7 or less. In addition, as the KES surface friction tester, a friction tester (KES-SE) manufactured by Katotech Co., Ltd. can be used, and the measurement of the static friction index can be performed, for example, by a method described later in Examples.

In order for the surface decoration layer to have a surface roughness SMD and a static friction index in the above-described range, for example, in addition to containing two or more types of inorganic fine particles satisfying the predetermined conditions, the amount of inorganic fine particles (inorganic fine particles The total amount, the amount of each inorganic fine particle), the particle diameter of each inorganic fine particle, the difference in the particle diameter of each inorganic fine particle, and the like, may be partially controlled, particularly preferably all of them.

The thickness of the surface decorative layer is not particularly limited, but usually the lower limit is preferably 0.6 µm, and more preferably 1.0 µm. Further, the upper limit of the film thickness of the surface decoration layer is preferably 100 µm, more preferably 80 µm, still more preferably 60 µm, and particularly preferably 20 µm. If the surface decorative layer is too thin, since it becomes difficult for the inorganic fine particles to be held in the surface decorative layer, the reduction of stickiness due to the inorganic fine particles may be insufficient, and the soft touch may be damaged. On the other hand, if the surface decoration layer is too thick, inorganic fine particles are completely buried in the surface decoration layer, and reduction of stickiness due to the inorganic fine particles cannot be expected, making it difficult to obtain a soft touch. In addition, there is a concern that curing failure of the curable resin compound or curling due to curing shrinkage may be caused. The film thickness of the surface decoration layer can be measured, for example, with a contact-type film thickness meter.

(Base film)

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

Polyesters preferably used as constituent resins of the base film are, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, or esters thereof, ethylene glycol, diethylene glycol, 1,4-butanediol , It can be prepared by polycondensing a glycol such as neopentyl glycol. In the polycondensation of aromatic dicarboxylic acid and glycol, a method of direct reaction, a method of polycondensation after transesterification reaction between an alkyl ester of an aromatic dicarboxylic acid and a glycol, or a method of polycondensation of a diglycol ester of an aromatic dicarboxylic acid An ordinary method such as a method of combining may be appropriately adopted. Representative examples of such polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and the like. These polyesters may be homopolymers or copolymers. In the case of a copolymer, it is preferable that the polyester units such as ethylene terephthalate units, butylene terephthalate units, and ethylene-2,6-naphthalate units are 70 mol% or more, more preferably 80 mol% or more, and even more preferably It is more than 90 mol%.

Although the base film may be an unstretched film, it is preferable that it is a stretched film from a viewpoint of the mechanical strength of the film for surface decoration. Although uniaxial stretching may be sufficient as stretching, or biaxial stretching may be sufficient, a biaxial stretched film is preferable from a 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 still more preferably 75 µm or more and 200 µm or less. If the base film is too thick, the moldability at the time of application to the decorative object may be deteriorated. In addition to the limited use, it is disadvantageous in terms of cost, and if it is too thin, the handling property of the resulting surface decoration film deteriorates. There is a tendency.

In addition, as described later, in the case of forming a print layer that imparts a pattern or color on the surface of the base film opposite to the surface decoration layer, 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 fear that the visibility of the printed layer viewed from the surface decoration layer side may become insufficient.

(Print layer, adhesive layer, etc.)

The film for surface decoration of the present invention may be provided with a printing layer that imparts a pattern or color on the surface of the base film on the side opposite to the surface decoration layer. Thereby, while providing excellent softness, it is possible to decorate a desired appearance.

The printing method is not particularly limited, and various printing methods such as thermal transfer, thermal transfer, sublimation transfer, intaglio printing, stencil printing, iron plate printing, lithographic printing, magnetism, electrostatic and inkjet methods can be applied.

Further, the film for surface decoration of the present invention may have an adhesive layer on the surface of the base film on the opposite side to the surface decoration layer. In this case, the film for surface decoration of the present invention can be attached to the resin molded body as a decoration object 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 for example, natural rubber, synthetic rubber, chloroprene rubber, NBR, butyl rubber, urethane rubber, vinyl acetate and copolymers thereof, acrylic acid and copolymers thereof, etc. Solvent type adhesive; Emulsion type adhesives such as natural rubber latex, chloroprene latex, NBR latex, vinyl acetate and copolymers thereof, acrylic acid and copolymers thereof; Water-soluble adhesives such as polyvinyl alcohol, starch, and glue; Thermosetting resins such as epoxy resins, polyester resins, urea and melamine resins, phenol resins, and polyurethane resins; Heat-melting adhesives such as paraffin wax, microcrystalline wax, asphalt, and resin wax mixtures; Polyolefins, such as polyethylene, and unsaturated polyester, etc. are mentioned. The adhesive may be one or two or more.

When the film for surface decoration 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 until the film for surface decoration of the present invention is attached to the resin molded body as a decoration object, and the release layer can be easily peeled off at the time of attachment. In addition, the release layer may be formed by, for example, applying a known release agent.

This application claims the benefit of priority based on Japanese Patent Application No. 2013-014817 for which it applied on January 29, 2013. The entire contents of the specification of Japanese Patent Application No. 2013-014817 for which it applied on January 29, 2013 is incorporated herein for reference.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is of course not limited by the following examples, and of course, the present invention is appropriately changed within a range suitable for the purpose of the earlier and later periods. It is possible, and they are all included in the technical scope of the present invention.

In addition, in the following, "%" and "parts" indicating the content rate and usage are based on mass unless otherwise specified.

The method of measuring the physical property values in Examples and Comparative Examples is as follows.

(Surface roughness SMD)

Using an automated surface tester (KES-FB4) manufactured by Katotech Co., Ltd., the variation in the upper and lower thickness of the sample surface (the surface decorative layer of the film) was measured. As a measurement condition, a load of 0.098 N was applied to a 0.5 mm diameter piano wire with a width of 5 mm, and the friction distance was 30 mm, the analysis distance was 20 mm, and the sample moving speed was 1 mm/sec. In addition, the measurement was performed in an environment of 20°C and 65% RH, and the average value of the five measurements was adopted.

(Stop friction index)

The surface friction coefficient was measured using a friction tester (KES-SE) manufactured by Kato Tech Co., Ltd. Measurement conditions are a bar of a standard friction ruler, a silicon sensor (10 mm x 10 mm x 3 mm) manufactured by Kato Tech Co., Ltd. is used as the friction material, and a load of 0.245 N/cm 2 (25 gf/cm 2) during friction, It was set as measurement sensitivity H (sensitivity 20 g/V). Other conditions such as friction distance and friction speed are as specified in the device specifications (friction distance 30 mm, analysis distance 20 mm, sample movement speed 1 mm/sec). Then, a data logger (a multi-input data collection system manufactured by Keyence Corporation) 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 member started to move was taken as a static friction index. In addition, the measurement was performed in an environment of 20°C and 65% RH, and the average value of the five measurements was adopted. In addition, the silicon sensor confirmed in advance that a value of 3 or more was obtained when a static friction index was measured using a commercially available biaxially stretched polyester film ("Soft Shine (registered trademark)" manufactured by Toyobo Corporation: thickness 125 μm) as a sample. Then, it was used for measurement.

(Average particle diameter)

Using a Coulter counter ("Multisizer II type" manufactured by Beckman Coulter), the particles were dispersed in a solvent that does not swell, and the volume average particle diameter was measured.

[Example 1]

On a biaxially oriented polyester film (“Soft Shine (registered trademark) TA009” manufactured by Toyobo, thickness 125 μm) containing co-polyester having an easily adhesive layer on both sides, a coating solution prepared by the following formulation , Apply with a wire bar so that the thickness of the coating layer after coating and curing becomes 3㎛, dry for 60 seconds with hot air at a temperature of 80℃, and then cure it under a high-pressure mercury lamp by the accumulated amount of light (200m) J/㎠ for surface decoration. I got a film. Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Preparation of coating solution]

The following materials were mixed in the mass ratio shown below, and stirred for 30 minutes or more to dissolve. Subsequently, a coating liquid was prepared by removing undissolved matter using a filter having a nominal filtration accuracy of 100 µm.

In addition, the average particle diameter of each inorganic fine particle contained in the coating liquid and the content ratio thereof 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% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

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

Inorganic fine particles ("Silo Jet P612" manufactured by Grace Davie Corporation, average particle diameter 12.0 µm): 1.000 mass%

Photoinitiator (currently BASF Japan ``Irgacure (registered trademark) 184''): 1.000% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

[Example 2]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

Methyl ethyl ketone: 41.646 mass%

Propylene glycol monomethyl ether: 27.764% by mass

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 9.255% by mass

Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Davie Corporation, average particle diameter 9.0 µm): 0.925% by mass

Inorganic fine particles ("Silo Jet P612" manufactured by Grace Davie Corporation, average particle diameter 12.0 µm): 0.925% by mass

Photoinitiator (currently, BASF Japan ``Irgacure (registered trademark) 184''): 0.925% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Example 3]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

Methyl ethyl ketone: 43.497 mass%

Propylene glycol monomethyl ether: 28.998% by mass

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

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

Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Davie Corporation, average particle diameter 9.0 µm): 0.925% by mass

Inorganic fine particles ("Silo Jet P612" manufactured by Grace Davie Corporation, average particle diameter 12.0 µm): 0.925% by mass

Photoinitiator (currently, BASF Japan ``Irgacure (registered trademark) 184''): 0.925% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Example 4]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Inorganic fine particles ("Syloid 72W" manufactured by Grace Davie Corporation, average particle diameter 3.0 µm): 0.800% by mass

Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Dabi Transfer, average particle diameter 9.0 µm): 0.900% by mass

Inorganic fine particles ("Silo Jet P616" manufactured by Grace Davie Corporation, average particle diameter 16.0 µm): 0.300 mass%

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Example 5]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Inorganic fine particles ("Syloid ED3" manufactured by Grace Davie Corporation, average particle diameter 5.0 µm): 0.440% by mass

Inorganic fine particles ("Syloid 74x5500" manufactured by Grace Davie Corporation, average particle diameter 8.0 µm): 0.958% by mass

Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Davie Corporation, average particle diameter 9.0 µm, 10% PGM dispersion): 0.240% by mass

Inorganic fine particles ("Silo Jet P612" manufactured by Grace Daby Corporation, average particle diameter 12.0 µm, 10% PGM dispersion): 0.360% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Example 6]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

-Inorganic fine particles ("Syloid W300" manufactured by Grace Dabi Transfer, average particle diameter 5.0 µm): 0.667 mass%

Inorganic fine particles ("Syloid W500" manufactured by Grace Davie Corporation, average particle diameter 8.0 µm): 0.667% by mass

Inorganic fine particles ("Syloid W900" manufactured by Grace Dabi Transfer, average particle diameter 13.0 µm): 0.667 mass%

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Example 7]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Inorganic fine particles ("Syloid 74x5500" manufactured by Grace Dabi Transfer, average particle diameter 8.0 µm): 1.000 mass%

Inorganic fine particles ("Syloid 74x6500" manufactured by Grace Davie Corporation, average particle diameter 6.0 µm): 0.500 mass%

Inorganic fine particles ("Syloid ED2" manufactured by Grace Dabi Transfer, average particle diameter 4.0 µm): 0.500 mass%

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Example 8]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Inorganic fine particles ("Silo Jet P616" manufactured by Grace Davie Corporation, average particle diameter 16.0 µm): 0.900% by mass

Inorganic fine particles ("Sicastar" manufactured by Core Front Co., Ltd., average particle diameter 50.0 µm): 0.300% by mass

Inorganic fine particles ("Cycasta" manufactured by Core Front, average particle diameter 20.0 µm): 0.800% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Comparative Example 1]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 41.297 mass%

Propylene glycol monomethyl ether: 27.531% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 5.985% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.197% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Comparative Example 2]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Davie Corporation, average particle diameter 9.0 µm): 1.999% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Comparative Example 3]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

-Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Davie Corporation, average particle diameter 9.0 µm): 1.000% by mass

Inorganic fine particles ("P409" manufactured by Grace Dabi Transfer, average particle diameter 9 µm): 1.000% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Comparative Example 4]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Inorganic fine particles ("P616" manufactured by Grace Dabi Transfer, average particle diameter 16 µm): 1.000% by mass

・Organic fine particles (Toyobo Corporation "Tuftic (registered trademark) YK-30", average particle diameter 33 µm): 1.000% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Comparative Example 5]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

-Methyl ethyl ketone: 43.178 mass%

Propylene glycol monomethyl ether: 28.786% by mass

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

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass

Organic fine particles (Toyobo Corporation "Tuftic (registered trademark) YK-80", average particle diameter of 80 µm): 1.999% by mass

Photoinitiator (currently BASF Japan ``Irgacure (registered trademark) 184''): 1.000% by mass

-Silicone surfactant (Toray Dow Corning ``DC57''): 0.050% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Comparative Example 6]

In Example 1, except having changed the prescription at the time of manufacturing a coating liquid as follows, it carried out similarly to Example 1, and obtained the film for surface decoration.

Methyl ethyl ketone: 42.000 mass%

Propylene glycol monomethyl ether: 27.750% by mass

Urethane acrylate UV/EB curing resin (Arakawa Chemical Co., Ltd. "Beam Set (registered trademark) 577", 3 to 6 functions, solid content 100% by mass): 11.000% by mass

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

Quaternary ammonium salt type cationic agent ("Acrit 1SX-1055" manufactured by Taisei Fine Chemical, weight average molecular weight 40,000, solid content 40% by mass): 3.200% by mass

Inorganic fine particles ("Syloid 74x4500" manufactured by Grace Davie Corporation, average particle diameter 9.0 µm): 4.000% by mass

Inorganic fine particles ("Silo Jet P612" manufactured by Grace Davie Corporation, average particle diameter 12.0 µm): 4.000% by mass

Photoinitiator (currently BASF Japan's "Irgacure (registered trademark) 184"): 1.000% by mass

-Silicone-based surfactant (Toray Dow Corning ``DC57''): 0.05% by mass

Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Reference Example 1]

Melamine resin (Sumitex (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.) on the side of the corona discharge treatment surface of a polyester film ("Crisper (registered trademark) G1211" manufactured by Toyobo, 50 µm thick) containing fine cavities inside. M-3") 10 parts by mass and 1 part by mass of a catalyst ("Sumitex (registered trademark) ACX" manufactured by Sumitomo Chemical Co., Ltd.) were mixed with 89 parts by mass of water, and 0.1 g/m 2 (when dried) It was applied and dried. On this coated surface, polyvinyl alcohol as a water-soluble resin ("GH-20" manufactured by Nippon Kose Chemical Co., Ltd.), melamine resin as a curing agent ("Sumitex (registered trademark) M-3" manufactured by Sumitomo Chemical Co., Ltd.), cationic substance Phosphorus cationic polyamide resin ("SR1005" manufactured by Sumitomo Chemical Industries, Ltd.), silica particles with an average particle diameter of 5 μm (“Silo Jet P405" manufactured by Grace Dabi Transfer Corporation), and silica particles with an average particle diameter of 12 μm (Grace Davision The company's "Silo Jet P412") was adjusted to a 10% aqueous solution so that the final solid content was 10/1/2//10/10 (mass ratio), coated with a wire bar, and heat treated in a gear oven at 140° C. for 4 minutes. Cured and dried. The coating amount was made to be 12 g/m 2, and a film for surface decoration was obtained. Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Reference Example 2]

10 mass of melamine resin ("Sumitex (registered trademark) M-3" manufactured by Sumitomo Chemical Industries, Ltd.) on the side of the corona discharge treatment surface of a polyester film ("Crisper (registered trademark) G1211" manufactured by Toyobo, 50 µm thick)) A coating liquid obtained by mixing 1 part by mass of a part and a catalyst ("Sumitex (registered trademark) ACX" manufactured by Sumitomo Chemical Industries, Ltd.) in 89 parts by mass of water was applied so as to be 0.1 g/m 2 (when dried) and dried. On this coated surface, polyvinyl alcohol as a water-soluble resin (“RS117” manufactured by Kurare), dimethylolhydroxyethylene urea resin as a curing agent (“SR5004” manufactured by Sumitomo Chemical Industries, Ltd.), and a cationic resin as a cationic substance (Nippon Gaya "Kayafix (registered trademark) UR" manufactured by Koo Corporation), silica particles having an average particle diameter of 5 µm ("Silo Jet P405" manufactured by Grace Daby Corporation), and silica particles having an average particle diameter of 12 µm ("Silo Jet P412 manufactured by Grace Davie Corporation") ”) as a final solid content of 10/3/1//10/10 (mass ratio), adjusted with a 10% aqueous solution, coated with a wire bar, and a hot air speed of 15 m/min, 100°C/120°C/140°C It was cured and dried by heat treatment for a total of 2 minutes every 30 seconds in the order of /120°C. The coating amount was made to be 14 g/m 2, and a film for surface decoration was obtained. Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Reference Example 3]

In Reference Example 2, as the polyester film, a polyester film ("Crisper (registered trademark) G1211" manufactured by Toyobo, 100 µm thick) was used, and a water-soluble resin, a curing agent, a cationic substance, and a silica having an average particle diameter of 5 µm. A film for surface decoration was obtained in the same manner as in Reference Example 2, except that the particles and silica particles having an average particle diameter of 12 µm were each used in a final solid content of 10/1/2//10/10 (mass ratio). Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

[Reference Example 4]

In Reference Example 2, instead of the polyester film containing fine cavities therein, a polypropylene film containing fine cavities therein ("Pearl Film Pyrene (registered trademark) P6255" manufactured by Toyobo, with a thickness of 120 µm) was used. , A water-soluble resin, a curing agent, a cationic substance, silica particles having an average particle diameter of 5 µm, and silica particles having an average particle diameter of 12 µm, respectively, as a final solid content of 10/1/1//10/10 (mass ratio), Further, a film for surface decoration was obtained in the same manner as in Reference Example 2 except that the drying temperature was set in the order of 80°C/100°C/120°C/100°C. Various physical properties (initial surface roughness (SMD) of the surface decoration layer, static friction index) in the obtained film for surface decoration were as shown in Table 2.

The following evaluation was performed about the film for surface decoration obtained by the above Example and a comparative example. The results are shown in Table 2.

(Initial tactile evaluation)

As subjects, 5 healthy women and 5 men (total 10) were collected from their teens to their 40s. Each of these subjects was placed in a constant temperature and humidity room humidified at 26°C 60% RH, and after being stabilized for about 30 minutes, an A4 sized surface decoration film was placed on a white side of thick paper ("Eco Cardboard EBA4100" manufactured by King Corporation) What was left standing on the image was presented, and only the surface (surface of the surface decoration layer) was freely touched with a fingertip or palm, and the touch of the surface was investigated. The question items are 4 items: ``Softness'', ``Dense'', ``No sticking feeling'' and ``Do you feel the feel of wood'' when you release your hand after placing your hand on the film surface. As, the determination was performed in four steps of "◎", "○", "△" and "x" based on the following determination criteria. And the result of the determination, which had the largest number of respondents among 10 subjects, was considered as the result of each sample. In addition, all of this initial touch evaluation was performed after storing the produced film for surface decoration for 10 days in a normal state (room temperature).

"Smooth"; ◎: The softness is very felt.

○: A soft feeling is felt.

△: The softness is slightly felt.

×: The softness is not felt.

"Fineness"; ◎: The texture is sufficiently felt.

○: A grain is felt.

?: The texture is slightly felt.

×: No grain is felt.

「No feeling of sticking to your hands」;◎: No feeling of sticking to your hands at all.

○: The feeling of sticking to the hand is not felt.

△: A feeling of sticking to the hand is slightly felt.

×: A feeling of sticking to the hand is felt.

"Do you feel the touch of wood?"; ◎: The feel of wood is very felt.

○: The feel of wood is felt.

?: The texture of wood is slightly felt.

X: The feel of wood is not felt.

(Change over time)

After subjecting the obtained surface decorative film to the following weathering test, the surface roughness (SMD) and static friction index of the surface decorative layer were measured again, and the surface roughness after the weathering test from the initial surface roughness (SMD) or static friction index ( SMD) or the value obtained by subtracting the static friction index (change value), and the film for surface decoration after the weathering test was evaluated for "smoothness" by the same method as the initial tactile evaluation. If the change value of the surface roughness (SMD) is ±0.1, it is the allowable range, and if the change value of the static friction index is ±0.4, it is the allowable range.

[Weather test]

According to JIS K 5400 (accelerated weather resistance), using a WEL-SUN-HCH B BR type sunshine super long life weather meter (manufactured by Suga Shikki Co., Ltd.), irradiation temperature 63°C, humidity 50% RH, for 18 minutes during a 120 minute cycle In 200 hours under conditions of rainfall, the surface decoration film as a sample was irradiated. After irradiation, the sample was air-dried for 5 hours or more in an atmosphere of 23°C and 50% RH.

From Table 2, the surface decorative film of the present invention obtained in the examples exhibits sufficient softness at the beginning of the decoration and makes the feel of wood feel, but the surface decorative film obtained in each comparative example has insufficient softness, You can see that it does not make you feel the texture of wood. In addition, the surface decorative film of the present invention obtained in each example has a small change over time and can maintain sufficient softness over a long period of time, but the surface decorative film obtained in each reference example has a large change over time, and the original softness of the decoration It can be seen that it is difficult to sustain the dryness for a long time.

The film for surface decoration of the present invention is useful, for example, for use in building materials, for interior applications such as vehicles and furniture, and for various molding applications in which surface decoration is performed using a film, and particularly, items that are frequently touched (cell phones, It is suitably used as a film for surface decoration for a mobile personal computer, a housing or member of an OA device or home appliance, an automobile interior member such as an instrument panel or a steering wheel, etc.).

Claims (8)

As a surface decoration film provided with a surface decoration layer on a base film,
The surface decoration 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 two or more inorganic fine particles satisfying the following conditions (i) to (iv). Consists of containing,
The total content of the inorganic fine particles is 5 to 35 parts by mass with respect to the total 100 parts by mass of the cured product of the curable resin compound and the cationic resin, and the surface decoration layer is a surface roughness SMD measured by a KES surface tester. A film for surface decoration excellent in softness, characterized in that 0.40㎛ or more and 2.0㎛ or less.
(i) the average particle diameter is in the range of 1.0 to 50㎛
(ii) The average particle diameter differs by 1.0 μm or more
(iii) The average particle diameter of the particles with the smallest average particle diameter is 1.0 μm or more and 16 μm or less.
(iv) The particles with the largest average particle diameter have an average particle diameter of 8 µm or more and 50 µm or less The film for surface decoration according to claim 1, wherein the surface decoration layer has a static friction index of 1.0 to 4.5 measured using a silicon sensor friction ruler with a KES surface friction tester. The film for surface decoration according to claim 1 or 2, wherein, of the inorganic fine particles contained in two or more types, the content of the particles having the smallest average particle diameter with respect to the total inorganic fine particles is 15% by mass or more and 85% by mass or less. The film for surface decoration according to claim 1 or 2, wherein, among the inorganic fine particles contained in two or more types, the content of the particles having the largest average particle diameter with respect to all inorganic fine particles is 15% by mass or more and 85% by mass or less. The film for surface decoration according to claim 1 or 2, wherein the content per one kind of the inorganic fine particles is 0.75 to 29.75 parts by mass with respect to 100 parts by mass of the total of the cured product of the curable resin compound and the cationic resin. The film for surface decoration according to claim 1 or 2, comprising 2 to 25 parts by mass of the cationic resin of the quaternary ammonium salt type based on 100 parts by mass of the cured product of the curable resin compound. The film for surface decoration according to claim 1 or 2, wherein the curable resin compound contains 5% by mass or more of a trifunctional or higher ionizing radiation curable resin compound. delete