WO2014119511A1 - Film for surface decoration - Google Patents
Film for surface decoration Download PDFInfo
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- WO2014119511A1 WO2014119511A1 PCT/JP2014/051667 JP2014051667W WO2014119511A1 WO 2014119511 A1 WO2014119511 A1 WO 2014119511A1 JP 2014051667 W JP2014051667 W JP 2014051667W WO 2014119511 A1 WO2014119511 A1 WO 2014119511A1
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- surface decoration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
Definitions
- the present invention relates to a film for surface decoration which can give a smooth touch.
- the tactile sensation required for the resin molded body varies depending on the appearance and the like.
- a smooth feel that is similar to genuine solid wood sometimes referred to herein as “smooth feeling”
- leather is imitated.
- a moist feel similar to real leather is desired.
- the present inventor has paid attention to “smooth feeling” among various tactile sensations, and previously proposed a decorative film capable of giving the feel of white wood to the surface of the resin molded body (Patent Document 1).
- a surface decorating layer comprising a water-soluble resin (A), a curing agent (B), a cationic substance (C) and particles (D) at a predetermined ratio is provided on the base film surface, It is a decorative film in which the coating amount and bulk density of the surface decorative layer are controlled within a specific range.
- This decorative film absorbs moisture on the surface of the molded body due to the hygroscopicity of the water-soluble resin itself, and by making the surface decorative layer porous structure by containing a large amount of particles, it produces a “smooth feeling”. It was something like that.
- the present invention has been made in view of the above circumstances, and the object thereof is for surface decoration that expresses a sufficient dry feeling at the beginning of decoration and can maintain a sufficient dry feeling over a long period of time.
- the “smooth feeling” in the present specification is a feeling that is not sticky to stick to the hand, and is expressed by having an appropriate fineness. Is approximated to the touch of solid wood not painted with paint or varnish.
- the present inventors made 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.
- two or more types of inorganic fine particles having an average particle size satisfying a predetermined condition are selected, and the surface roughness SMD measured by the KES surface tester is set appropriately. It has been found that if the fineness can be controlled within a predetermined range, the smoothness at the beginning of decoration can be improved and the sustainability can be improved, and the present invention has been completed.
- the present invention has the following configuration.
- a surface decorating film comprising a surface decorating layer on a substrate film, wherein the surface decorating layer comprises a cured product of a curable resin compound and a weight average molecular weight of 20,000 to 100, Quaternary ammonium salt type cationic resin, and two or more inorganic fine particles satisfying the following conditions (i) to (iv), and the surface decoration layer is made of KES:
- the average particle diameter is in the range of 1.0 to 50 ⁇ m.
- the average particle diameter is different by 1.0 ⁇ m or more.
- the average particle diameter of the smallest average particle diameter is 1.0 ⁇ m or more and 16 ⁇ m or less.
- the average particle size of particles having the largest average particle size is 8 ⁇ m or more and 50 ⁇ m or less.
- the surface decoration layer is a static friction index measured using a silicon sensor friction element with a KES surface friction tester. The film for surface decorating according to the above (1), wherein is from 1.0 to 4.5.
- the total content of the inorganic fine particles is 5 to 35 parts by mass with respect to a total of 100 parts by mass of the cured product of the curable resin compound and the cationic resin.
- the film for surface decoration of description (4) Among the inorganic fine particles contained in two or more kinds, the content of 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. ) For surface decoration. (5) Among the inorganic fine particles contained in two or more kinds, the content of particles having the largest average particle diameter is from 15% by mass to 85% by mass with respect to the total inorganic fine particles. ) For surface decoration. (6) 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 in total of the cured product of the curable resin compound and the cationic resin (1 ) To (5).
- the surface decorating film of the present invention it is possible to express a sufficient smooth feeling at the beginning of decoration and to maintain a sufficient smooth feeling even for a long period of time.
- the smooth feeling produced by the surface decorating film of the present invention is a tactile sensation like that of unpainted solid wood.
- the molded product becomes more approximate, and the commercial value can be increased.
- this commercial value increases further.
- Such a surface decoration film of the present invention is useful for, for example, building materials, interior applications such as vehicles and furniture, and various molding processing applications that perform surface decoration using a film. It is suitably used as a surface decorating film for articles that are frequently touched by hand (mobile phones, mobile personal computers, OA equipment and housings and members of home appliances, automobile interior members such as instrument panels and handles).
- the surface decorating film of the present invention is provided with a surface decorating layer on at least one surface of a base film, and imparts a smooth touch to the surface of a decorating object (resin molded body, etc.) It is a decorative film excellent in feeling.
- the surface decoration layer in this invention contains the hardened
- 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 ray, radiation, electron beam, etc.) Ionizing radiation curable resin compounds that are cured by irradiation and thermosetting resin compounds that are cured by heat, and preferably ionizing radiation curable resin compounds.
- a surface decoration layer is comprised with the hardened
- the ionizing radiation curable resin compound examples include an ultraviolet curable urethane (meth) acrylate resin, an ultraviolet curable polyester (meth) acrylate resin, an ultraviolet curable epoxy (meth) acrylate resin, and a raw material compound such as (meta ) Acrylic ionizing radiation curable resin compounds.
- an ultraviolet curable urethane acrylate resin is preferable.
- the ionizing radiation curable resin compound preferably includes a trifunctional or higher functional ionizing radiation curable resin compound, and it is preferable to use a bifunctional ionizing radiation curable resin compound in combination as necessary.
- the surface decoration layer can be provided with moderate hardness and flexibility.
- 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 is preferably 95% by mass or less.
- the bifunctional (meth) acrylate ionizing radiation curable resin compound has two or more alcoholic hydroxyl groups in one molecule.
- a compound in which the hydroxyl group of the polyhydric alcohol having 2 is an esterified product of two (meth) acrylic acids can be used.
- (D) (Meth) acrylic acid diesters of ethylene oxide or propylene oxide adduct of bisphenol A or bisphenol A hydride: 2,2′-bis (4-acryloxyethoxyphenyl) propane, 2,2′-bis ( 4-acryloxypropoxyphenyl) propane, etc.
- (E) In a molecule obtained by 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 two (meth) acryloyloxy groups (F) Epoxy (meth) acrylates having two (meth) acryloyloxy groups in the molecule obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid, etc. Can be mentioned.
- a (meth) acrylate ionizing radiation curable resin compound as the ionizing radiation curable resin compound, as the trifunctional or higher functional (meth) acrylate 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.
- thermosetting resin compounds include thermosetting urethane resins, thermosetting acrylic resins, thermosetting silicone resins, thermosetting polyester resins, thermosetting vinyl ester resins, thermosetting epoxy resins, and thermosetting resins.
- thermosetting resin compounds include thermosetting urethane resins, thermosetting acrylic resins, thermosetting silicone resins, thermosetting polyester resins, thermosetting vinyl ester resins, thermosetting epoxy resins, and thermosetting resins.
- a phenol resin etc. are mentioned.
- a thermosetting urethane resin is particularly preferable.
- thermosetting urethane resin examples include, for example, polyester-type polyurethane, polyether-type polyurethane, polycarbonate-type polyurethane, polyether-polycarbonate-type polyurethane, and the like, and these polyurethanes are modified with other polymers having different skeletons (for example, silicone). Modified, fluorine polymer modified, polyacrylate polymer modified) and the like.
- the cationic resin contained in the surface decorative 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 “specific cationic resin”). Yes).
- specific cationic resin having a molecular weight in this specific range, the surface decorative layer exhibits high hydrophilicity, so that it easily absorbs moisture from the palm that touched the surface decorative layer. Helps to develop a smooth feel and allows the smooth feel to be sustained over a long period of time.
- Examples of the quaternary ammonium salt type cationic resin used as the specific cationic resin include alkyl halides such as dimethylaminoalkyl methacrylate (for example, dimethylaminoethyl methacrylate) and dimethylaminoalkylacrylamide (for example, dimethylaminopropylacrylamide).
- alkyl halides such as dimethylaminoalkyl methacrylate (for example, dimethylaminoethyl methacrylate) and dimethylaminoalkylacrylamide (for example, dimethylaminopropylacrylamide).
- Examples thereof include a resin obtained by copolymerizing a monomer such as a salt (for example, a methyl chloride salt) with a (meth) acrylic acid ester monomer (preferably a methacrylic ester).
- 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, and further preferably 77,000 or less. is there.
- the weight average molecular weight of the specific cationic resin can be measured by, for example, 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 with respect to 100 parts by mass of the cured product of the curable resin compound. It is as follows. If the content of the specific cationic resin is too small, it is difficult to maintain the smooth feeling over a long period of time. If the content is too large, the surface strength may be reduced, or the appearance may be abnormal due to the bleeding out of the cationic resin.
- the inorganic fine particles contained in the surface decoration layer of the present invention mainly give difficulty in sticking to the surface decoration layer and help to realize a smooth touch. Further, by selecting and containing two or more inorganic particles having an average particle diameter satisfying a predetermined condition, it is possible to maintain a smooth feeling over a long period of time.
- the inorganic fine particles satisfy the following (i) to (iv).
- the average particle diameter is in the range of 1.0 to 50 ⁇ m (preferably in the range of 3.0 to 30 ⁇ m, more preferably in the range of 6.0 to 15 ⁇ m).
- the average particle diameters are different from each other by 1.0 ⁇ m or more (preferably 2.0 ⁇ m or more, more preferably 3.0 ⁇ m or more).
- the average particle size of the smallest average particle size is 1.0 ⁇ m to 16 ⁇ m (preferably 3.0 ⁇ m to 15 ⁇ m, more preferably 6.0 ⁇ m to 13 ⁇ m).
- the average particle size of particles having the largest average particle size is 8 ⁇ m or more and 50 ⁇ m or less (preferably 10 m or more and 30 ⁇ m or less, more preferably 12 ⁇ m or more and 20 ⁇ m or less).
- the average particle size of the inorganic fine particles in the present invention is The volume average particle diameter measured by the Coulter counter method is meant.
- the average particle diameter of two or more inorganic fine particles is to be obtained simultaneously, the average particle diameter of each particle is obtained by separating the peaks detected overlapping each other.
- the difference in the average particle diameter which is a requirement of the above (ii), is preferably as large as possible, and particularly preferably 3.0 ⁇ m or more.
- the type of 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, and benzoguanamine particles. Among these, silicon dioxide and talc are preferable.
- the shape of the inorganic fine particles is not particularly limited, and any shape such as a sphere, a flat plate, a rod, an indeterminate shape, or a different aspect ratio can be used. From the viewpoint of easy formation, amorphous particles are preferable. In the present invention, at least two 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. Good.
- 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, 100 parts by mass in total of the cured product of the curable resin compound and the specific cationic resin. 5.5 parts by mass or more and 30 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, the smooth touch tends to be insufficient. On the other hand, if the total content of the inorganic fine particles is too large, it tends to be a rough and unpleasant tactile sensation that is far from the smooth feeling. In addition, the particles are likely to fall off, and the dry tactile sensation is likely to change, making it difficult to maintain the smooth feeling for a long period of time. Furthermore, the surface decoration layer may become brittle and formability may be reduced.
- Content per 1 type of the said inorganic type fine particle is 0.75 mass part or more and 29.75 mass parts or less with respect to 100 mass parts in total of the hardened
- the content of the smallest average particle diameter with respect to the total inorganic fine particles is preferably 15% by mass or more and 85% by mass or less, more preferably 17% by mass. % Or more and 75% by mass or less.
- grains with the largest average particle diameter among the said inorganic fine particles contained 2 or more types is 15 to 85 mass%, More preferably, it is 17 masses. % Or more and 75% by mass or less. If there are too few particles with the smallest average particle size or particles with the largest average particle size, the smooth touch tends to be insufficient.
- the surface decoration layer may become brittle and formability may be reduced.
- photopolymerization initiator examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, and 4,4.
- the addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 parts by weight or more and 15 parts by weight or less, and more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the ionizing radiation curable resin compound. 10 parts by mass or less. If the amount of the photopolymerization initiator is too small, it may take a long time to cure and the productivity may be reduced. If the amount is too large, the surface decorating layer may be yellowed by the photopolymerization initiator.
- thermosetting resin compound When a thermosetting resin compound is used as the curable resin compound, it is preferable to add a cross-linking agent to the coating liquid when forming the surface decoration layer.
- cross-linking agent examples include isocyanate-based cross-linking agents such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred from the viewpoint of superiority.
- an epoxy type crosslinking agent, an oxazoline type crosslinking agent, a carbodiimide type crosslinking agent, a melamine type crosslinking agent, etc. can also be used according to the functional group which a thermosetting resin compound has.
- One type of crosslinking agent may be sufficient and 2 or more types may be sufficient as it.
- the addition amount of the crosslinking agent is not particularly limited, but is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the thermosetting resin compound. It is as follows. If the amount of the crosslinking agent is too small, it may take a long time to cure and the productivity may be lowered. If the amount is too large, the resin may be hard and brittle.
- the coating liquid used for forming the surface decoration layer may further contain a conventionally known surfactant as a leveling agent within a range that does not impair the effects of the present invention.
- a conventionally known surfactant as a leveling agent within a range that does not impair the effects of the present invention.
- the surface tension of a coating liquid can be lowered
- the coating liquid at the time of forming a surface decoration layer can contain a well-known additive suitably other than the surfactant mentioned above.
- the surface decorating layer is, for example, an appropriate organic solvent containing the above-described curable resin compound, inorganic fine particles, cationic resin, and various additives (photopolymerization initiator, cross-linking agent, leveling agent, etc.) contained as necessary. It can be formed by adding a coating liquid to the coating liquid, applying the coating liquid on a base film, and performing a drying and curing treatment.
- organic solvent examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; propylene glycol monomethyl ether And glycol ether solvents such as propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as toluene and xylene; and the like. These organic solvents can be used alone or in admixture of two or more.
- the application method of the coating liquid when forming the surface decoration layer includes 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
- Known coating methods such as a lip coating method, a roll-to-roll method can be applied, and a gravure coating method that can be uniformly applied is preferable, and a reverse gravure method is particularly preferable. preferable. What is necessary is just to set the application quantity of a coating liquid suitably according to the film thickness etc. of the desired surface decoration layer.
- coating a coating liquid is not restrict
- the irradiation amount of active rays for curing the compound is preferably 50 mJ / cm 2 or more, more preferably 1000 mJ / cm 2 or less, more preferably as an integrated light amount. It is 150 mJ / cm 2 or more and 700 mJ / cm 2 or less.
- the integrated light amount is too small, the polymerization reaction of the ionizing radiation curable resin compound is not promoted and the surface hardness tends to be remarkably reduced.
- the base film may be deformed due to the influence of the generated heat. .
- the heating temperature for curing it is preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. If 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 be remarkably reduced. If it is too high, the substrate film may be deformed. In addition, the heating at the time of hardening may serve as drying after apply
- the surface decoration layer formed as described above has a surface roughness SMD measured by a KES surface tester of 0.4 ⁇ m or more and 2.0 ⁇ m or less.
- KES KawabatavaluEvaluation SYSTEM
- the surface roughness SMD of the surface decoration layer is within the above range, the texture becomes moderately fine, and a smooth feeling like genuine unpainted solid wood can be expressed.
- the surface roughness SMD of the surface decoration layer is preferably 0.45 ⁇ m or more and 1.7 ⁇ m or less, more preferably 0.55 ⁇ m or more and 1.4 ⁇ m or less.
- KES surface tester an automated surface tester (KES-FB4) manufactured by Kato Tech Co., Ltd. can be used, and the surface roughness SMD can be measured, for example, by the method described later in Examples. .
- the surface decoration layer preferably has a static friction index of 1.0 to 4.5 measured with a KES surface friction tester using a silicon sensor friction element.
- the static friction index is an index indicating whether or not the film is sticky and does not stick to the hand.
- the static friction index of the surface decoration layer is preferably 1.2 or more and 4.0 or less, more preferably 1.3 or more and 3.7 or less.
- a friction tester manufactured by Kato Tech Co., Ltd. can be used, and the static friction index can be measured by the method described later in the examples, for example.
- the inorganic fine particles In order to make the surface decoration layer have the surface roughness SMD and the static friction index within the above-mentioned range, for example, in addition to containing two or more kinds of inorganic fine particles satisfying the above-mentioned predetermined conditions, the inorganic fine particles
- the total amount of the inorganic fine particles total amount of inorganic fine particles, the amount of each inorganic fine particle), the particle diameter of each inorganic fine particle, the particle size difference of each inorganic fine particle, etc., particularly preferably all may be controlled. .
- the film thickness of the surface decorative layer is not particularly limited, but usually the lower limit is preferably 0.6 ⁇ m, more preferably 1.0 ⁇ m. Moreover, 100 micrometers is preferable, as for the upper limit of the film thickness of a surface decoration layer, 80 micrometers is more preferable, 60 micrometers is further more preferable, and 20 micrometers is especially preferable. If the surface decorating layer is too thin, the inorganic fine particles are hardly held in the surface decorating layer, so that the reduction of stickiness due to the inorganic fine particles becomes insufficient, and the dry feel may be impaired.
- the film thickness of a surface decoration layer can be measured with a contact-type film thickness meter, for example.
- the base film is not particularly limited, but a plastic film is preferable.
- the resin constituting the base film include polyester, polyolefin, polyamide, polyurethane, polyether, polystyrene, polyacrylic resin, and polyvinyl resin. Among these, polyester is particularly preferable.
- Polyesters preferably used as the constituent resin of the base film include, for example, aromatic dicarboxylic acids or esters thereof such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol. It can be produced by polycondensation with glycols such as For polycondensation of aromatic dicarboxylic acid and glycol, a method of direct reaction, a method of transesterification of alkyl ester of aromatic dicarboxylic acid and glycol and polycondensation, or diglycol ester of aromatic dicarboxylic acid is used.
- aromatic dicarboxylic acids or esters thereof such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol. It can be produced by poly
- polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and the like. These polyesters may be homopolymers or copolymers.
- the polyester unit such as ethylene terephthalate unit, butylene terephthalate unit, ethylene-2,6-naphthalate unit is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol%. That's it.
- the base film may be an unstretched film, but is preferably a stretched film from the viewpoint of the mechanical strength of the surface decorating 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 ⁇ m or more and 350 ⁇ m or less, more preferably 50 ⁇ m or more and 260 ⁇ m or less, and further preferably 75 ⁇ m or more and 200 ⁇ m or less. If the base film is too thick, the formability when applied to the object to be decorated may be reduced, and the usage is limited. In addition, it is disadvantageous in terms of cost. There exists a tendency for the handleability of a film to worsen.
- the base film when providing the printing layer which provides a pattern and a color on the base film surface side opposite to the surface decoration layer as mentioned later, has a total light transmittance of 80% or more. Is preferred. If the total light transmittance of the base film is too low, the visibility of the printed layer viewed from the surface decorating layer side may be insufficient.
- the film for surface decorating of this invention may be equipped with the printing layer which provides a pattern and a color on the base film surface side on the opposite side to a surface decorating layer. Thereby, it is possible to decorate a desired appearance while giving an excellent smooth feeling.
- the printing method is not particularly limited, and various printing methods such as thermal transfer, thermal transfer, sublimation transfer, intaglio printing, stencil printing, letterpress printing, planographic printing, magnetism, electrostatic and ink jet methods can be applied.
- the surface decorating film of the present invention may include an adhesive layer on the surface of the base film opposite to the surface decorating layer.
- the surface decorating film of the present invention can be affixed to the resin molding to be decorated by the adhesive strength of the adhesive layer.
- the pressure-sensitive adhesive that can be used for forming the pressure-sensitive adhesive layer is not particularly limited.
- natural rubber, synthetic rubber, chloroprene rubber, NBR, butyl rubber, urethane rubber, vinyl acetate and its copolymer, acrylic acid and Solvent adhesives such as copolymers
- Emulsion adhesives such as natural rubber latex, chloroprene latex, NBR latex, vinyl acetate and copolymers thereof, acrylic acid and copolymers thereof
- thermosetting resins such as epoxy resins, polyester resins, urea and melamine resins, phenol resins, polyurethane resins
- hot-melt adhesives such as paraffin wax, microcrystalline wax, asphalt, resin wax mixtures
- Polyolefin such as polyethylene, unsaturated Riesuteru; and the like. 1 type may be sufficient as an adhesive and 2 or more types may be sufficient as it.
- the surface decorating film of the present invention has the adhesive layer
- the adhesive force of the adhesive layer can be protected with a release layer until the film for surface decoration of the present invention is attached to a resin molded object to be decorated. Can be easily peeled off.
- the release layer may be formed, for example, by applying a known release agent.
- the measuring method of physical property values in Examples and Comparative Examples is as follows.
- Surface roughness SMD Using an automated surface tester (KES-FB4) manufactured by Kato Tech Co., Ltd., the variation in the vertical thickness of the sample surface (film surface decoration layer) was measured. Measurement conditions were as follows: a load of 0.098 N was applied to a 0.5 mm diameter piano wire having a width of 5 mm, a friction distance of 30 mm, an analysis distance of 20 mm, and a sample moving speed of 1 mm / sec. The measurement was performed in an environment of 20 ° C. and 65% RH, and an average value of five measurements was adopted.
- 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 element started moving was used as a static friction index.
- the measurement was performed in an environment of 20 ° C. and 65% RH, and an average value of five measurements was adopted.
- the silicon sensor was 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 Co., Ltd .: thickness 125 ⁇ m) as a sample. And used for measurement.
- Example 1 On a biaxially oriented polyester film (“Soft Shine (registered trademark) TA009” manufactured by Toyobo, thickness 125 ⁇ m) containing a copolyester having an easy-adhesion layer on both sides, a coating solution prepared by the following formulation was applied and cured. Coating using a wire bar so that the thickness of the coating layer is 3 ⁇ m, drying with hot air at a temperature of 80 ° C. for 60 seconds, and then curing with a cumulative light quantity of 200 mJ / cm 2 under a high-pressure mercury lamp, Got.
- Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
- Example 2 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 41.646% by mass Propylene glycol monomethyl ether: 27.764% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content 100% by mass): 18.509% by mass Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 9.255% by mass Inorganic fine particles (“Spheroid 74 ⁇ 4500” manufactured by GRACE Davison, average particle size: 9.0 ⁇ m): 0.925% by mass Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison,
- Example 3 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.497% by mass Propylene glycol monomethyl ether: 28.998% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content 100% by mass): 18.509% by mass Quaternary ammonium salt type cation agent (“Papiogen (registered trademark) P105” manufactured by Senka Co., Ltd., weight average molecular weight 20,000, solid content 60% by mass): 6.170% by mass Inorganic fine particles (“Spheroid 74 ⁇ 4500” manufactured by GRACE Davison, average particle size: 9.0 ⁇ m): 0.925% by mass Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison, average
- Example 4 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Inorganic fine particles (“S
- Example 5 a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Inorganic fine
- Example 6 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Inorganic fine
- Example 7 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass ⁇ Inorgan
- Example 8 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Inorganic fine
- Example 1 a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 41.297% by mass Propylene glycol monomethyl ether: 27.531% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content 100% by mass): 14.364% by mass -Urethane acrylate UV / EB cured resin (Arakawa Chemical Industries “Beamset (registered trademark) 271”, bifunctional, solid content 100% by mass): 9.576% by mass Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 5.985% by mass Photopolymerization initiator (current
- Example 2 In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Inorganic fine
- Example 3 a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass ⁇ In
- Example 4 a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Inorganic
- Example 5 a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 43.178% by mass Propylene glycol monomethyl ether: 28.786% by mass -Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577” manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass -Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass% Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass Organic fine particles
- Example 6 (Comparative Example 6) In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows. ⁇ Methyl ethyl ketone: 42.000 mass% Propylene glycol monomethyl ether: 27.750% by mass -Urethane acrylate UV / EB cured resin ("Beam Set (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content: 100% by mass): 11.000% by mass -Urethane acrylate UV / EB curable resin ("Arkagawa Chemical Industries” Beamset (registered trademark) 271 ", bifunctional, solid content 100% by mass): 7.000% by mass Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 3.200% by mass Inorganic
- a melamine resin (“Smitex (registered trademark) M-” manufactured by Sumitomo Chemical Co., Ltd.) is disposed on the corona discharge treated side of a polyester film ("Chrisper (registered trademark) G1211” manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m) containing fine cavities inside. 3 ") 10 parts by weight and a coating solution (1 part by weight of" Sumitex (registered trademark) ACX “manufactured by Sumitomo Chemical Co., Ltd.)) mixed with 89 parts by weight of water was 0.1 g / m 2 (when dried). It was applied and dried.
- polyvinyl alcohol (“GH-20” manufactured by Nippon Synthetic Chemical Co., Ltd.) as a water-soluble resin
- melamine resin Synitomo Chemical Co., Ltd.
- a cationic polyamide resin (“SR1005” manufactured by Sumitomo Chemical Co., Ltd.) which is a cationic substance, silica particles having an average particle diameter of 5 ⁇ m (“Silojet P405” manufactured by GRACEDavison), and silica particles having an average particle diameter of 12 ⁇ m (GRACEDAvison) "Silojet P412") was adjusted to a 10% aqueous solution so that the final solid content would be 10/1/2 // 10/10 (mass ratio), coated with a wire bar, and 140 ° C gear oven And then cured by drying for 4 minutes and dried. The coating amount was 12 g / m 2 to obtain a surface decorating film.
- Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
- polyvinyl alcohol (“RS117” manufactured by Kuraray Co., Ltd.) which is a water-soluble resin, dimethylol hydroxyethylene urea resin (“SR5004” manufactured by Sumitomo Chemical Co., Ltd.) which is a curing agent, and cation which is a cationic substance.
- Resin (“Kayafix (registered trademark) UR” manufactured by Nippon Kayaku Co., Ltd.), silica particles having an average particle size of 5 ⁇ m (“Silojet P405” manufactured by GRACEDavison) and silica particles having an average particle size of 12 ⁇ m (“Silojet manufactured by GRACEDavison”) P412 ”) is adjusted to a 10% aqueous solution so that the final solid content is 10/3/1 // 10/10 (mass ratio), coated with a wire bar, and heated at 100 m at a hot air speed of 15 m / min. / 120 ° C / 140 ° C / 120 ° C in order of heat treatment every 30 seconds for a total of 2 minutes. Dried. The coating amount was 14 g / m 2 to obtain a surface decorating film.
- Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
- Reference Example 3 In Reference Example 2, as a polyester film, a polyester film (“Crisper (registered trademark) G1211” manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m) is used, a water-soluble resin, a curing agent, a cationic substance, silica particles having an average particle diameter of 5 ⁇ m, and average particles A film for surface decoration was prepared in the same manner as in Reference Example 2 except that silica particles having a diameter of 12 ⁇ m were used so that the final solid content was 10/1/2 // 10/10 (mass ratio). Obtained. Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
- SMD initial surface roughness
- static friction index of the surface decoration layer were as shown in Table 2.
- Reference Example 4 In Reference Example 2, instead of a polyester film containing fine cavities inside, a polypropylene film containing fine cavities inside (“Pearl Film Pyrene (registered trademark) P6255” thickness 120 ⁇ m, manufactured by Toyobo Co., Ltd.), A water-soluble resin, a curing agent, a cationic substance, silica particles having an average particle diameter of 5 ⁇ m, and silica particles having an average particle diameter of 12 ⁇ m are each 10/1/1 // 10/10 (mass ratio) in terms of the final solid content.
- a surface decorating film was obtained in the same manner as in Reference Example 2 except that the drying temperature was set to 80 ° C / 100 ° C / 120 ° C / 100 ° C in this order.
- Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
- all of this initial tactile sensation evaluation was performed after storing the produced film for surface decoration in a normal state (normal temperature) for 10 days.
- the obtained surface decoration film was subjected to the following weather resistance test, and then the surface roughness (SMD) and static friction index of the surface decoration layer were measured again, and the weather resistance was determined from the initial surface roughness (SMD) or static friction index.
- the surface roughness after the test (SMD) or the value obtained by subtracting the static friction index (change value) was determined, and the “smooth feeling” was evaluated by the same method as the initial tactile sensation evaluation for the surface decoration film after the weather resistance test. .
- the change value of the surface roughness (SMD) is acceptable if it is ⁇ 0.1
- the change value of the static friction index is acceptable if it is ⁇ 0.4.
- the film for surface decorating of the present invention obtained in each example expresses a sufficiently smooth feeling at the beginning of decorating and gives the feel of wood feel, but is obtained in each comparative example. It can be seen that the surface-decorating film has a dull feeling and does not give the feel of wood. Moreover, the surface decorating film of the present invention obtained in each example has a small change over time and can maintain a sufficient smooth feeling over a long period of time, but for the surface decorating obtained in each reference example. It can be seen that the film has a large change over time and it is difficult to maintain the smooth feeling at the beginning of decoration for a long period of time.
- the surface decorating film of the present invention is useful for, for example, building materials, interiors such as vehicles and furniture, and various molding processing applications that perform surface decorating using a film. It is suitably used as a surface decorating film for articles (cell phones, mobile personal computers, OA equipment and housings and members of home appliances, automobile interior members such as instrument panels and handles).
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
ところが、樹脂成形体に所望の(例えば無垢木材を模した)外観を付与しても、実際に触れた際に感じられる触感が外観から想像される触感(例えば無垢木材を模した場合では、さらさらとした触感)とかけ離れていては、消費者の本物志向に合わず、商品価値を十分に高めることはできない。 2. Description of the Related Art Conventionally, the surface of various resin moldings such as automobile interior parts, electrical appliance housings, and building materials has been decorated with films, and various decorative films are known. However, many of them improve the appearance (so-called appearance) by giving gloss, color, pattern, etc., and most of the decorative films aiming to give a desired feel to the surface of the resin molded body It was not reported.
However, even if a desired appearance (for example, imitating solid wood) is imparted to the resin molded body, the tactile sensation that is actually felt when touched can be imagined from the appearance (for example, in the case of imitating solid wood, If it is far from the tactile sensation), it does not match the consumer's real intention and the product value cannot be sufficiently increased.
なお、本明細書で言う「さらさら感」とは、具体的には、手に貼り付くようなべたつき感がなく、適度なキメ細かさを有することにより発現される感覚であり、無垢木材(詳しくは塗料やニス等で塗装されていない無垢木材)の触感に近似したものである。 The present invention has been made in view of the above circumstances, and the object thereof is for surface decoration that expresses a sufficient dry feeling at the beginning of decoration and can maintain a sufficient dry feeling over a long period of time. To provide a film.
In addition, the “smooth feeling” in the present specification is a feeling that is not sticky to stick to the hand, and is expressed by having an appropriate fineness. Is approximated to the touch of solid wood not painted with paint or varnish.
(1)基材フィルム上に表面加飾層を備えた表面加飾用フィルムであって、前記表面加飾層が、硬化性樹脂化合物の硬化物と、重量平均分子量が20,000~100,000である第4級アンモニウム塩タイプのカチオン系樹脂と、下記条件(i)~(iv)を満足する2種以上の無機系微粒子とを含有してなり、かつ前記表面加飾層は、KES表面試験機で測定される表面粗さSMDが0.40μm以上、2.0μm以下であることを特徴とするさらさら感に優れた表面加飾用フィルム。
(i)平均粒子径が1.0~50μmの範囲内にあること
(ii)平均粒子径がそれぞれ1.0μm以上異なっていること
(iii)最も平均粒子径の小さい粒子の平均粒子径が1.0μm以上16μm以下であること
(iv)最も平均粒子径の大きい粒子の平均粒子径が8μm以上50μm以下であること
(2)前記表面加飾層は、KES表面摩擦試験機でシリコンセンサー摩擦子を用いて測定される静摩擦指標が1.0~4.5である前記(1)に記載の表面加飾用フィルム。
(3)前記無機系微粒子の総含有量が、前記硬化性樹脂化合物の硬化物および前記カチオン系樹脂の合計100質量部に対して5~35質量部である前記(1)または(2)に記載の表面加飾用フィルム。
(4)2種以上含有される前記無機系微粒子のうち、最も平均粒子径の小さい粒子の、全無機系微粒子に対する含有量が15質量%以上85質量%以下である前記(1)~(3)のいずれかに記載の表面加飾用フィルム。
(5)2種以上含有される前記無機系微粒子のうち、最も平均粒子径の大きい粒子の、全無機系微粒子に対する含有量が15質量%以上85質量%以下である前記(1)~(4)のいずれかに記載の表面加飾用フィルム。
(6)前記無機系微粒子1種当たりの含有量が、前記硬化性樹脂化合物の硬化物および前記カチオン系樹脂の合計100質量部に対して0.75~29.75質量部である前記(1)~(5)のいずれかに記載の表面加飾用フィルム。
(7)前記第4級アンモニウム塩タイプのカチオン系樹脂を、前記硬化性樹脂化合物の硬化物100質量部に対して2~25質量部含む前記(1)~(6)のいずれかに記載の表面加飾用フィルム。
(8)前記硬化性樹脂化合物は、3官能以上の電離放射線硬化型樹脂化合物を5質量%以上含む前記(1)~(7)のいずれかに記載の表面加飾用フィルム。 That is, the present invention has the following configuration.
(1) A surface decorating film comprising a surface decorating layer on a substrate film, wherein the surface decorating layer comprises a cured product of a curable resin compound and a weight average molecular weight of 20,000 to 100, Quaternary ammonium salt type cationic resin, and two or more inorganic fine particles satisfying the following conditions (i) to (iv), and the surface decoration layer is made of KES: A surface-decorating film excellent in a dry feeling, characterized in that the surface roughness SMD measured by a surface testing machine is 0.40 μm or more and 2.0 μm or less.
(i) The average particle diameter is in the range of 1.0 to 50 μm.
(ii) The average particle diameter is different by 1.0 μm or more.
(iii) The average particle diameter of the smallest average particle diameter is 1.0 μm or more and 16 μm or less.
(iv) The average particle size of particles having the largest average particle size is 8 μm or more and 50 μm or less. (2) The surface decoration layer is a static friction index measured using a silicon sensor friction element with a KES surface friction tester. The film for surface decorating according to the above (1), wherein is from 1.0 to 4.5.
(3) In the above (1) or (2), the total content of the inorganic fine particles is 5 to 35 parts by mass with respect to a total of 100 parts by mass of the cured product of the curable resin compound and the cationic resin. The film for surface decoration of description.
(4) Among the inorganic fine particles contained in two or more kinds, the content of 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. ) For surface decoration.
(5) Among the inorganic fine particles contained in two or more kinds, the content of particles having the largest average particle diameter is from 15% by mass to 85% by mass with respect to the total inorganic fine particles. ) For surface decoration.
(6) 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 in total of the cured product of the curable resin compound and the cationic resin (1 ) To (5).
(7) The quaternary ammonium salt type cationic resin according to any one of the above (1) to (6), which contains 2 to 25 parts by mass with respect to 100 parts by mass of the cured product of the curable resin compound. Surface decoration 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 functional ionizing radiation curable resin compound.
本発明の表面加飾用フィルムが発現させるさらさら感は、未塗装の無垢木材のような触感であるので、例えば外観についても木目調の印刷を施すなどの加飾を施せば、本物の無垢木材により近似した成形品となり、商品価値を高めることができる。しかも、本発明の表面加飾用フィルムが発現させるさらさら感は長期間にわたって持続するので、この商品価値は更に高まる。 According to the surface decorating film of the present invention, it is possible to express a sufficient smooth feeling at the beginning of decoration and to maintain a sufficient smooth feeling even for a long period of time.
The smooth feeling produced by the surface decorating film of the present invention is a tactile sensation like that of unpainted solid wood. Thus, the molded product becomes more approximate, and the commercial value can be increased. And since the smooth feeling which the film for surface decoration of this invention expresses lasts for a long period of time, this commercial value increases further.
本発明における表面加飾層は、硬化性樹脂化合物の硬化物と、カチオン系樹脂と、2種以上の無機系微粒子とを含有してなり、例えば、硬化性樹脂化合物、カチオン系樹脂および2種以上の無機系微粒子を含有する塗布液を基材フィルム上に塗布し、乾燥および硬化処理を施すことにより形成される。 (Surface decoration layer)
The surface decoration layer in this invention contains the hardened | cured material of a curable resin compound, cationic resin, and 2 or more types of inorganic microparticles, for example, curable resin compound, cationic resin, and 2 types It is formed by applying a coating solution containing the above inorganic fine particles on a substrate film, and performing drying and curing treatments.
(a)炭素数2~12のアルキレングリコールの(メタ)アクリル酸ジエステル類:エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6-ヘキサンジオール(メタ)アクリレートなど、
(b)ポリオキシアルキレングリコールの(メタ)アクリレート酸ジエステル類:ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレートなど、
(c)多価アルコールの(メタ)アクリル酸ジエステル類:ペンタエリスリトールジ(メタ)アクリレートなど、
(d)ビスフェノールAあるいはビスフェノールAの水素化物のエチレンオキシド又はプロピレンオキシド付加物の(メタ)アクリル酸ジエステル類:2,2’-ビス(4-アクリロキシエトキシフェニル)プロパン、2,2’-ビス(4-アクリロキシプロポキシフェニル)プロパンなど、
(e)多価イソシアネート化合物と2個以上のアルコール性水酸基含有化合物を予め反応させて得られる末端イソシアネート基含有化合物に、更にアルコール性水酸基含有(メタ)アクリレートを反応させて得られる、分子内に2個の(メタ)アクリロイルオキシ基を有するウレタン(メタ)アクリレート類、
(f)分子内に2個以上のエポキシ基を有する化合物にアクリル酸又はメタクリル酸を反応させて得られる分子内に2個の(メタ)アクリロイルオキシ基を有するエポキシ(メタ)アクリレート類、などが挙げられる。 When a (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 has two or more alcoholic hydroxyl groups in one molecule. For example, a compound in which the hydroxyl group of the polyhydric alcohol having 2 is an esterified product of two (meth) acrylic acids can be used. In particular,
(A) (Meth) acrylic acid diesters of alkylene glycols 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 diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc.
(C) Polyhydric alcohol (meth) acrylic acid diesters: pentaerythritol di (meth) acrylate, etc.
(D) (Meth) acrylic acid diesters of ethylene oxide or propylene oxide adduct of bisphenol A or bisphenol A hydride: 2,2′-bis (4-acryloxyethoxyphenyl) propane, 2,2′-bis ( 4-acryloxypropoxyphenyl) propane, etc.
(E) In a molecule obtained by 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 two (meth) acryloyloxy groups,
(F) Epoxy (meth) acrylates having two (meth) acryloyloxy groups in the molecule obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid, etc. Can be mentioned.
(a)ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレートなど、
(b)多価イソシアネート化合物と2個以上のアルコール性水酸基含有化合物を予め反応させて得られる末端イソシアネート基含有化合物に、更にアルコール性水酸基含有(メタ)アクリレートを反応させて得られる、分子内に3個以上の(メタ)アクリロイルオキシ基を有するウレタン(メタ)アクリレート類、
(c)分子内に3個以上のエポキシ基を有する化合物にアクリル酸又はメタクリル酸を反応させて得られる、分子内に3個以上の(メタ)アクリロイルオキシ基を有するエポキシ(メタ)アクリレート類、などが挙げられる。 In the case of using a (meth) acrylate ionizing radiation curable resin compound as the ionizing radiation curable resin compound, as the trifunctional or higher functional (meth) acrylate 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) In a 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 three or more (meth) acryloyloxy groups,
(C) epoxy (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule, obtained by reacting a compound having 3 or more epoxy groups in the molecule with acrylic acid or methacrylic acid, Etc.
特定カチオン系樹脂の重量平均分子量は、好ましくは30,000以上、より好ましくは33,000以上であり、好ましくは90,000以下、より好ましくは80,000以下、さらに好ましくは77,000以下である。特定カチオン系樹脂の重量平均分子量は例えば液体クロマトグラフ質量分析法で測定することができる。 Examples of the quaternary ammonium salt type cationic resin used as the specific cationic resin include alkyl halides such as dimethylaminoalkyl methacrylate (for example, dimethylaminoethyl methacrylate) and dimethylaminoalkylacrylamide (for example, dimethylaminopropylacrylamide). Examples thereof include a resin obtained by copolymerizing a monomer such as a salt (for example, a methyl chloride salt) with a (meth) acrylic acid ester monomer (preferably a methacrylic ester). Commercially available products include, for example, cationic agents such as the Acrit series manufactured by Taisei Fine Chemical Co., Ltd., the Papiogen (registered trademark) series manufactured by Senka Co., Ltd., and the Unisense series.
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, and further preferably 77,000 or less. is there. The weight average molecular weight of the specific cationic resin can be measured by, for example, liquid chromatography mass spectrometry.
(i)平均粒子径が1.0~50μmの範囲内(好ましくは3.0~30μmの範囲内、より好ましくは6.0~15μmの範囲内)にあること
(ii)平均粒子径がそれぞれ1.0μm以上(好ましくは2.0μm以上、より好ましくは3.0μm以上)異なっていること
(iii)最も平均粒子径の小さい粒子の平均粒子径が1.0μm以上16μm以下(好ましくは3.0μm以上15μm以下、より好ましくは6.0μm以上13μm以下)であること
(iv)最も平均粒子径の大きい粒子の平均粒子径が8μm以上50μm以下(好ましくは10m以上30μm以下、より好ましくは12μm以上20μm以下)であること
なお本発明における無機系微粒子の平均粒子径は、コールターカウンター法で測定される体積平均粒子径を意味するものである。
本発明において2以上の無機系微粒子の平均粒子径を同時に求めようとする場合、各粒子の平均粒子径は重なって検出されるピークを分離して求めることになるが、この時のピーク分離のし易さを考慮すると、上記(ii)の要件である平均粒子径の差は、大きいほど好ましく、特に3.0μm以上であるのがよい。 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) The average particle diameters are 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 size of the smallest average particle size is 1.0 μm to 16 μm (preferably 3.0 μm to 15 μm, more preferably 6.0 μm to 13 μm).
(iv) The average particle size of particles having the largest average particle size is 8 μm or more and 50 μm or less (preferably 10 m or more and 30 μm or less, more preferably 12 μm or more and 20 μm or less). The average particle size of the inorganic fine particles in the present invention is The volume average particle diameter measured by the Coulter counter method is meant.
In the present invention, when the average particle diameter of two or more inorganic fine particles is to be obtained simultaneously, the average particle diameter of each particle is obtained by separating the peaks detected overlapping each other. In consideration of easiness, the difference in the average particle diameter, which is a requirement of the above (ii), is preferably as large as possible, and particularly preferably 3.0 μm or more.
なお本発明においては、少なくとも平均粒子径が異なる2種以上の無機系微粒子を用いればよく、2種以上の無機系微粒子の種類や形状は、それぞれ同じであってもよいし、異なっていてもよい。 The type of 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, and benzoguanamine particles. Among these, silicon dioxide and talc are preferable. The shape of the inorganic fine particles is not particularly limited, and any shape such as a sphere, a flat plate, a rod, an indeterminate shape, or a different aspect ratio can be used. From the viewpoint of easy formation, amorphous particles are preferable.
In the present invention, at least two 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. Good.
基材フィルムは、特に限定されるものではないが、好ましくはプラスティックフィルムがよい。基材フィルムを構成する樹脂としては、例えば、ポリエステル、ポリオレフィン、ポリアミド、ポリウレタン、ポリエーテル、ポリスチレン、ポリアクリル系樹脂、ポリビニル系樹脂等が挙げられ、これらの中でも特にポリエステルが好ましい。 (Base 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, and polyvinyl resin. Among these, polyester is particularly preferable.
本発明の表面加飾用フィルムは、表面加飾層とは反対側の基材フィルム表面に、模様や色を付与する印刷層を備えていてもよい。これにより、優れたさらさら感を与えると同時に、所望の外観を加飾することができる。
印刷方法としては、特に制限はなく、感熱転写、熱転写、昇華転写、凹版印刷、孔版印刷、凸版印刷、平版印刷、磁気、静電、及びインクジェット法など各種印刷方法が適用可能である。 (Printing layer, adhesive layer, etc.)
The film for surface decorating of this invention may be equipped with the printing layer which provides a pattern and a color on the base film surface side on the opposite side to a surface decorating layer. Thereby, it is possible to decorate a desired appearance while giving an excellent smooth feeling.
The printing method is not particularly limited, and various printing methods such as thermal transfer, thermal transfer, sublimation transfer, intaglio printing, stencil printing, letterpress printing, planographic printing, magnetism, electrostatic and ink jet methods can be applied.
なお以下において、含有率および使用量を表す「%」及び「部」は、特記しない限り質量基準である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
In the following, “%” and “parts” representing the content and the amount used are based on mass unless otherwise specified.
(表面粗さSMD)
カトーテック(株)製の自動化表面試験機(KES-FB4)を用いて、試料表面(フィルムの表面加飾層)の上下厚み変動を測定した。測定条件は5mm幅の0.5mm径ピアノ線に0.098Nの荷重をかけ、摩擦距離30mm、解析距離20mm、試料移動速度1mm/secとした。なお測定は20℃65%RH環境下で行い、5回測定の平均値を採用した。 The measuring method of physical property values in Examples and Comparative Examples is as follows.
(Surface roughness SMD)
Using an automated surface tester (KES-FB4) manufactured by Kato Tech Co., Ltd., the variation in the vertical thickness of the sample surface (film surface decoration layer) was measured. Measurement conditions were as follows: a load of 0.098 N was applied to a 0.5 mm diameter piano wire having a width of 5 mm, a friction distance of 30 mm, an analysis distance of 20 mm, and a sample moving speed of 1 mm / sec. The measurement was performed in an environment of 20 ° C. and 65% RH, and an average value of five measurements was adopted.
カトーテック(株)製の摩擦感テスター(KES-SE)を用いて、表面摩擦係数を測定した。測定条件は、標準摩擦子のバーを使用し、摩擦子にカトーテック(株)製のシリコンセンサー(10mm×10mm×3mm)を用い、摩擦時の荷重0.245N/cm2(25gf/cm2)、測定感度H(感度20g/V)とした。摩擦距離、摩擦速度等その他の条件は装置仕様通りである(摩擦距離30mm、解析距離20mm、試料移動速度1mm/sec)。そして、摩擦感テスターにデータロガー(キーエンス社製マルチ入力データ収集システム)を繋ぎ、測定時に得られる荷重の電圧値を取得し、摩擦子が動き出した時点の電圧値を静摩擦指標とした。なお測定は20℃65%RH環境下で行い、5回測定の平均値を採用した。またシリコンセンサーは、市販の二軸延伸ポリエステルフィルム(東洋紡社製「ソフトシャイン(登録商標)」:厚み125μm)を試料として静摩擦指標を測定したときに3以上の値が得られる事を予め確認してから、測定に使用した。 (Static friction index)
The surface friction coefficient was measured using a friction tester (KES-SE) manufactured by Kato Tech Co., Ltd. The measurement conditions were as follows: a standard friction bar was used, a silicon sensor (10 mm × 10 mm × 3 mm) manufactured by Kato Tech Co., Ltd. was used for the friction, and a load at the time of friction of 0.245 N / cm 2 (25 gf / cm 2). ) And measurement sensitivity H (sensitivity 20 g / V). Other conditions such as the friction distance and the friction speed are as specified in the apparatus specifications (friction distance 30 mm, analysis distance 20 mm, sample moving 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 element started moving was used as a static friction index. The measurement was performed in an environment of 20 ° C. and 65% RH, and an average value of five measurements was adopted. The silicon sensor was 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 Co., Ltd .: thickness 125 μm) as a sample. And used for measurement.
コールターカウンター(ベックマン・コールター社製「マルチサイザーII型」)を用いて、粒子を膨潤させない溶媒に分散させて、体積平均粒子径を測定した。 (Average particle size)
Using a Coulter counter (“Multisizer II type” manufactured by Beckman Coulter, Inc.), the particles were dispersed in a solvent that does not swell, and the volume average particle diameter was measured.
両面に易接着層を有する共重合ポリエステルを含む二軸配向ポリエステルフィルム(東洋紡製「ソフトシャイン(登録商標)TA009」、厚み125μm)上に、下記の処方で調製した塗布液を、塗布硬化後の塗布層の厚みが3μmになるようにワイヤーバーを用いて塗布し、温度80℃の熱風で60秒間乾燥した後、高圧水銀灯下、積算光量200mJ/cm2により硬化させて、表面加飾用フィルムを得た。得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 1)
On a biaxially oriented polyester film (“Soft Shine (registered trademark) TA009” manufactured by Toyobo, thickness 125 μm) containing a copolyester having an easy-adhesion layer on both sides, a coating solution prepared by the following formulation was applied and cured. Coating using a wire bar so that the thickness of the coating layer is 3 μm, drying with hot air at a temperature of 80 ° C. for 60 seconds, and then curing with a cumulative light quantity of 200 mJ / cm 2 under a high-pressure mercury lamp, Got. Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
下記の材料を下記に示す質量比で混合し、30分以上攪拌して溶解させた。次いで、公称ろ過精度が100μmのフィルターを用いて未溶解物を除去することにより、塗布液を調製した。
なお、塗布液に含まれる各無機系微粒子の平均粒子径とその含有比は表1に示す通りとなる(以下の実施例、比較例においても、同様)。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):1.000質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP612」、平均粒子径12.0μm):1.000質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量% [Preparation of coating solution]
The following materials were mixed at the mass ratio shown below, and dissolved by stirring for 30 minutes or more. Next, a coating solution was prepared by removing undissolved substances using a filter having a nominal filtration accuracy of 100 μm.
In addition, the average particle diameter and content ratio of each inorganic fine particle 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% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
・ Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 1.000% by mass
Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison, average particle size: 12.0 μm): 1.000% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:41.646質量%
・プロピレングリコールモノメチルエーテル:27.764質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):18.509質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):9.255質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):0.925質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP612」、平均粒子径12.0μm):0.925質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):0.925質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 2)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 41.646% by mass
Propylene glycol monomethyl ether: 27.764% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content 100% by mass): 18.509% by mass
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 9.255% by mass
Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 0.925% by mass
Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison, average particle size 12.0 μm): 0.925% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 0.925% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.497質量%
・プロピレングリコールモノメチルエーテル:28.998質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):18.509質量%
・第4級アンモニウム塩タイプカチオン剤(センカ社製「パピオゲン(登録商標)P105」、重量平均分子量20,000、固形分60質量%):6.170質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):0.925質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP612」、平均粒子径12.0μm):0.925質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):0.925質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 3)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.497% by mass
Propylene glycol monomethyl ether: 28.998% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content 100% by mass): 18.509% by mass
Quaternary ammonium salt type cation agent (“Papiogen (registered trademark) P105” manufactured by Senka Co., Ltd., weight average molecular weight 20,000, solid content 60% by mass): 6.170% by mass
Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 0.925% by mass
Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison, average particle size 12.0 μm): 0.925% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 0.925% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイド72W」、平均粒子径3.0μm):0.800質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):0.900質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP616」、平均粒子径16.0μm):0.300質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 Example 4
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Inorganic fine particles (“Syloid 72W” manufactured by GRACEDavison, average particle size: 3.0 μm): 0.800% by mass
Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 0.900% by mass
Inorganic fine particles (“Silojet P616” manufactured by GRACE Davison, average particle diameter 16.0 μm): 0.300 mass%
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイドED3」、平均粒子径5.0μm):0.440質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x5500」、平均粒子径8.0μm):0.958質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm、10%PGM分散):0.240質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP612」、平均粒子径12.0μm、10%PGM分散):0.360質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 5)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Inorganic fine particles (“Spheroid ED3” manufactured by GRACEDavison, average particle size: 5.0 μm): 0.440% by mass
Inorganic fine particles (“Spheroid 74 × 5500” manufactured by GRACE Davison, average particle size 8.0 μm): 0.958% by mass
Inorganic fine particles (“Syloid 74 × 4500” manufactured by GRACE Davison, average particle size 9.0 μm, 10% PGM dispersion): 0.240% by mass
Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison, average particle size 12.0 μm, 10% PGM dispersion): 0.360% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイドW300」、平均粒子径5.0μm):0.667質量%
・無機系微粒子(GRACEDavison社製「サイロイドW500」、平均粒子径8.0μm):0.667質量%
・無機系微粒子(GRACEDavison社製「サイロイドW900」、平均粒子径13.0μm):0.667質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 6)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Inorganic fine particles (“Syloid W300” manufactured by GRACE Davison, average particle size: 5.0 μm): 0.667% by mass
Inorganic fine particles (“Syloid W500” manufactured by GRACE Davison, average particle size 8.0 μm): 0.667% by mass
Inorganic fine particles (“Syloid W900” manufactured by GRACE Davison, average particle size 13.0 μm): 0.667% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x5500」、平均粒子径8.0μm):1.000質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x6500」、平均粒子径6.0μm):0.500質量%
・無機系微粒子(GRACEDavison社製「サイロイドED2」、平均粒子径4.0μm):0.500質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 7)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
・ Inorganic fine particles (“Spheroid 74 × 5500” manufactured by GRACE Davison, average particle size 8.0 μm): 1.000% by mass
Inorganic fine particles (“Spheroid 74 × 6500” manufactured by GRACE Davison, average particle size 6.0 μm): 0.500% by mass
Inorganic fine particles (“Syloid ED2” manufactured by GRACEDavison, average particle size: 4.0 μm): 0.500% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP616」、平均粒子径16.0μm):0.900質量%
・無機系微粒子(コアフロント社製「sicastar」、平均粒子径50.0μm):0.300質量%
・無機系微粒子(コアフロント社製「sicastar」、平均粒子径20.0μm):0.800質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Example 8)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Inorganic fine particles (“Silojet P616” manufactured by GRACE Davison, average particle size 16.0 μm): 0.900 mass%
Inorganic fine particles (“sicastar” manufactured by Corefront Corporation, average particle size 50.0 μm): 0.300% by mass
Inorganic fine particles (“sicastar” manufactured by Corefront Corporation, average particle size 20.0 μm): 0.800% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:41.297質量%
・プロピレングリコールモノメチルエーテル:27.531質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):14.364質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):9.576質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):5.985質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.197質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Comparative Example 1)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 41.297% by mass
Propylene glycol monomethyl ether: 27.531% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content 100% by mass): 14.364% by mass
-Urethane acrylate UV / EB cured resin (Arakawa Chemical Industries “Beamset (registered trademark) 271”, bifunctional, solid content 100% by mass): 9.576% by mass
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 5.985% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.197% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):1.999質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Comparative Example 2)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 1.999% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):1.000質量%
・無機系微粒子(GRACEDavison社製「P409」、平均粒子径9μm):1.000質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Comparative Example 3)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
・ Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 1.000% by mass
Inorganic fine particles (“P409” manufactured by GRACE Davison, average particle size 9 μm): 1.000% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・無機系微粒子(GRACEDavison社製「P616」、平均粒子径16μm):1.000質量%
・有機系微粒子(東洋紡社製「タフチック(登録商標)YK-30」、平均粒子径33μm):1.000質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Comparative Example 4)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Inorganic fine particles (“P616” manufactured by GRACE Davison, average particle size 16 μm): 1.000% by mass
Organic fine particles (“Toughtic (registered trademark) YK-30” manufactured by Toyobo Co., Ltd., average particle size: 33 μm): 1.000% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:43.178質量%
・プロピレングリコールモノメチルエーテル:28.786質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.994質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.996質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):4.998質量%
・有機系微粒子(東洋紡社製「タフチック(登録商標)YK-80」、平均粒子径80μm):1.999質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.050質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Comparative Example 5)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 43.178% by mass
Propylene glycol monomethyl ether: 28.786% by mass
-Urethane acrylate UV / EB cured resin ("Beamset (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functional, solid content 100% by mass): 11.994% by mass
-Urethane acrylate UV / EB curable resin ("A BEACH SET (registered trademark) 271", bifunctional, solid content 100 mass%) manufactured by Arakawa Chemical Industries, Ltd .: 7.996 mass%
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 4.998% by mass
Organic fine particles (“Toughtic (registered trademark) YK-80” manufactured by Toyobo Co., Ltd., average particle size 80 μm): 1.999% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
Silicone surfactant (“DC57” manufactured by Toray Dow Corning): 0.050% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
実施例1において、塗布液を調製する際の処方を下記の通りに変更したこと以外は、実施例1と同様にして、表面加飾用フィルムを得た。
・メチルエチルケトン:42.000質量%
・プロピレングリコールモノメチルエーテル:27.750質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)577」、3~6官能、固形分100質量%):11.000質量%
・ウレタンアクリレート系UV/EB硬化樹脂(荒川化学工業社製「ビームセット(登録商標)271」、2官能、固形分100質量%):7.000質量%
・第4級アンモニウム塩タイプカチオン剤(大成ファインケミカル社製「アクリット1SX-1055」、重量平均分子量40,000、固形分40質量%):3.200質量%
・無機系微粒子(GRACEDavison社製「サイロイド74x4500」、平均粒子径9.0μm):4.000質量%
・無機系微粒子(GRACEDavison社製「サイロジェットP612」、平均粒子径12.0μm):4.000質量%
・光重合開始剤(現BASFジャパン社製「イルガキュア(登録商標)184」):1.000質量%
・シリコーン系界面活性剤(東レ・ダウコーニング社製「DC57」):0.05質量%
得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Comparative Example 6)
In Example 1, a film for surface decorating was obtained in the same manner as in Example 1 except that the formulation for preparing the coating liquid was changed as follows.
・ Methyl ethyl ketone: 42.000 mass%
Propylene glycol monomethyl ether: 27.750% by mass
-Urethane acrylate UV / EB cured resin ("Beam Set (registered trademark) 577" manufactured by Arakawa Chemical Industry Co., Ltd., 3-6 functionalities, solid content: 100% by mass): 11.000% by mass
-Urethane acrylate UV / EB curable resin ("Arkagawa Chemical Industries" Beamset (registered trademark) 271 ", bifunctional, solid content 100% by mass): 7.000% by mass
Quaternary ammonium salt type cation agent (“Acryt 1SX-1055” manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 40,000, solid content 40% by mass): 3.200% by mass
Inorganic fine particles (“Spheroid 74 × 4500” manufactured by GRACE Davison, average particle size: 9.0 μm): 4.00% by mass
Inorganic fine particles (“Silojet P612” manufactured by GRACE Davison, average particle size: 12.0 μm): 4.00% by mass
Photopolymerization initiator (currently “Irgacure (registered trademark) 184” manufactured by BASF Japan): 1.000% by mass
-Silicone surfactant ("DC57" manufactured by Toray Dow Corning): 0.05% by mass
Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
内部に微細な空洞を含有するポリエステルフィルム(東洋紡社製「クリスパー(登録商標)G1211」厚み50μm)のコロナ放電処理面側に、メラミン樹脂(住友化学工業社製「スミテックス(登録商標)M-3」)10質量部および触媒(住友化学工業社製「スミテックス(登録商標)ACX」)1質量部を水89質量部に混合した塗布液を、0.1g/m2(乾燥時)になるように塗布し、乾燥した。この塗布面の上に、水溶性樹脂であるポリビニルアルコール(日本合成化学社製「GH-20」)、硬化剤であるメラミン樹脂(住友化学工業社製「スミテックス(登録商標)M-3」)、カチオン性物質であるカチオン性ポリアミド樹脂(住友化学工業社製「SR1005」)、平均粒子径5μmのシリカ粒子(GRACEDavison社製「サイロジェットP405」)及び平均粒子径12μmのシリカ粒子(GRACEDavison社製「サイロジェットP412」)をそれぞれ最終固形分で10/1/2//10/10(質量比)となるように、10%水溶液に調整し、ワイヤーバーでコートし、140℃のギアオーブンで4分間熱処理することにより硬化させ乾燥した。塗布量は12g/m2となるようにし、表面加飾用フィルムを得た。得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Reference Example 1)
A melamine resin ("Smitex (registered trademark) M-" manufactured by Sumitomo Chemical Co., Ltd.) is disposed on the corona discharge treated side of a polyester film ("Chrisper (registered trademark) G1211" manufactured by Toyobo Co., Ltd., thickness 50 μm) containing fine cavities inside. 3 ") 10 parts by weight and a coating solution (1 part by weight of" Sumitex (registered trademark) ACX "manufactured by Sumitomo Chemical Co., Ltd.)) mixed with 89 parts by weight of water was 0.1 g / m 2 (when dried). It was applied and dried. On this coated surface, polyvinyl alcohol (“GH-20” manufactured by Nippon Synthetic Chemical Co., Ltd.) as a water-soluble resin, and melamine resin (“Smitex (registered trademark) M-3” manufactured by Sumitomo Chemical Co., Ltd.) as a curing agent are provided. ), A cationic polyamide resin (“SR1005” manufactured by Sumitomo Chemical Co., Ltd.) which is a cationic substance, silica particles having an average particle diameter of 5 μm (“Silojet P405” manufactured by GRACEDavison), and silica particles having an average particle diameter of 12 μm (GRACEDAvison) "Silojet P412") was adjusted to a 10% aqueous solution so that the final solid content would be 10/1/2 // 10/10 (mass ratio), coated with a wire bar, and 140 ° C gear oven And then cured by drying for 4 minutes and dried. The coating amount was 12 g / m 2 to obtain a surface decorating film. Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
ポリエステルフィルム(東洋紡社製「クリスパー(登録商標)G1211」厚み50μm)のコロナ放電処理面側に、メラミン樹脂(住友化学工業社製「スミテックス(登録商標)M-3」)10質量部および触媒(住友化学工業社製「スミテックス(登録商標)ACX」)1質量部を水89質量部に混合した塗布液を、0.1g/m2(乾燥時)になるように塗布し、乾燥した。この塗布面の上に、水溶性樹脂であるポリビニルアルコール(クラレ社製「RS117」)、硬化剤であるジメチロールヒドロキシエチレン尿素樹脂(住友化学工業社製「SR5004」)、カチオン性物質であるカチオン性樹脂(日本化薬社製「カヤフィクス(登録商標)UR」)、平均粒子径5μmのシリカ粒子(GRACEDavison社製「サイロジェットP405」)及び平均粒子径12μmのシリカ粒子(GRACEDavison社製「サイロジェットP412」)をそれぞれ最終固形分で10/3/1//10/10(質量比)となるように、10%水溶液に調整し、ワイヤーバーでコートし、熱風速度15m/分で、100℃/120℃/140℃/120℃の順で30秒ごとに合計2分間熱処理することにより硬化させ乾燥した。塗布量は14g/m2となるようにし、表面加飾用フィルムを得た。得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Reference Example 2)
10 parts by mass of melamine resin (“Smitex (registered trademark) M-3” manufactured by Sumitomo Chemical Co., Ltd.) and catalyst on the corona discharge treatment side of a polyester film (“Chrisper (registered trademark) G1211” manufactured by Toyobo Co., Ltd., 50 μm thick) (“SUMITEX (registered trademark) ACX” manufactured by Sumitomo Chemical Co., Ltd.) A coating solution prepared by mixing 1 part by mass with 89 parts by mass of water was applied to a dry weight of 0.1 g / m 2 and dried. . On this coated surface, polyvinyl alcohol (“RS117” manufactured by Kuraray Co., Ltd.) which is a water-soluble resin, dimethylol hydroxyethylene urea resin (“SR5004” manufactured by Sumitomo Chemical Co., Ltd.) which is a curing agent, and cation which is a cationic substance. Resin (“Kayafix (registered trademark) UR” manufactured by Nippon Kayaku Co., Ltd.), silica particles having an average particle size of 5 μm (“Silojet P405” manufactured by GRACEDavison) and silica particles having an average particle size of 12 μm (“Silojet manufactured by GRACEDavison”) P412 ") is adjusted to a 10% aqueous solution so that the final solid content is 10/3/1 // 10/10 (mass ratio), coated with a wire bar, and heated at 100 m at a hot air speed of 15 m / min. / 120 ° C / 140 ° C / 120 ° C in order of heat treatment every 30 seconds for a total of 2 minutes. Dried. The coating amount was 14 g / m 2 to obtain a surface decorating film. Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
参考例2において、ポリエステルフィルムとして、ポリエステルフィルム(東洋紡社製「クリスパー(登録商標)G1211」厚み100μm)を用い、水溶性樹脂、硬化剤、カチオン性物質、平均粒子径5μmのシリカ粒子及び平均粒子径12μmのシリカ粒子をそれぞれ最終固形分で10/1/2//10/10(質量比)となるように用いたこと以外は、参考例2と同様の方法で、表面加飾用フィルムを得た。得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Reference Example 3)
In Reference Example 2, as a polyester film, a polyester film (“Crisper (registered trademark) G1211” manufactured by Toyobo Co., Ltd., thickness 100 μm) is used, a water-soluble resin, a curing agent, a cationic substance, silica particles having an average particle diameter of 5 μm, and average particles A film for surface decoration was prepared in the same manner as in Reference Example 2 except that silica particles having a diameter of 12 μm were used so that the final solid content was 10/1/2 // 10/10 (mass ratio). Obtained. Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
参考例2において、内部に微細な空洞を含有するポリエステルフィルムの代わりに、内部に微細な空洞を含有するポリプロピレンフィルム(東洋紡社製「パールフィルム パイレン(登録商標)P6255」厚み120μm)を使用し、水溶性樹脂、硬化剤、カチオン性物質、平均粒子径5μmのシリカ粒子及び平均粒子径12μmのシリカ粒子をそれぞれ最終固形分で10/1/1//10/10(質量比)となるように用い、かつ乾燥温度を80℃/100℃/120℃/100℃の順とした以外は、参考例2と同様の方法で、表面加飾用フィルムを得た。得られた表面加飾用フィルムにおける各種物性(表面加飾層の初期の表面粗さ(SMD)、静摩擦指標)は表2に示すとおりであった。 (Reference Example 4)
In Reference Example 2, instead of a polyester film containing fine cavities inside, a polypropylene film containing fine cavities inside (“Pearl Film Pyrene (registered trademark) P6255” thickness 120 μm, manufactured by Toyobo Co., Ltd.), 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 are each 10/1/1 // 10/10 (mass ratio) in terms of the final solid content. A surface decorating film was obtained in the same manner as in Reference Example 2 except that the drying temperature was set to 80 ° C / 100 ° C / 120 ° C / 100 ° C in this order. Various physical properties (initial surface roughness (SMD) and static friction index of the surface decoration layer) of the obtained film for surface decoration were as shown in Table 2.
(初期触感評価)
被験者として10歳代から40歳代までの健康な女子5名男子5名(計10名)を集めた。これら被験者を1名ずつ、26℃60%RHに調湿した恒温恒湿室に入室させ、約30分間安静にさせた後、A4版サイズの表面加飾用フィルムを厚紙(キングコーポレーション社製「エコボール紙EBA4100」)の白色面上に静置したものを呈示し、その表面(表面加飾層の面)のみを指先または掌により自由に触らせて、その表面の触感について質問調査した。質問項目は、「さらさら感」、「キメの細かさ」、フィルム表面に手を置いた後、手を放した時に感じられる「手への貼り付き感のなさ」、および「木材の触感が感じられるか」の4項目として、判定は下記の判定基準に基づき「◎」、「○」、「△」、「×」の4段階で行った。そして被験者10名のうちもっとも回答人数の多かった判定結果を各試料の結果とみなした。なお、この初期触感評価はいずれも、作製した表面加飾用フィルムを10日間、通常の状態(常温)で保管した後に行った。 The following evaluation was performed about the film for surface decoration obtained by the above Example and the comparative example. The results are shown in Table 2.
(Initial tactile evaluation)
As subjects, 5 healthy girls and 5 boys (10 people in total) from 10 to 40 years old were collected. Each of these subjects entered a constant temperature and humidity chamber adjusted to 26 ° C. and 60% RH and allowed to rest for about 30 minutes, and then a surface decoration film of A4 size was made of cardboard (manufactured by King Corporation “ Eco-cardboard paper EBA4100 ") that was allowed to stand on a white surface was presented, and only the surface (surface of the decorative layer) was freely touched with a fingertip or palm, and the surface texture was questioned. The questions included “feeling smooth”, “fineness of texture”, “no feeling of sticking to the hand” and “feeling of wood feel” when you put your hand on the film surface and then release it. As the four items of “Can be done”, the determination was performed in four stages of “「 ”,“ ◯ ”,“ Δ ”, and“ × ”based on the following criteria. And the judgment result with the largest number of respondents among the 10 subjects was regarded as the result of each sample. In addition, all of this initial tactile sensation evaluation was performed after storing the produced film for surface decoration in a normal state (normal temperature) for 10 days.
○:さらさら感が感じられる
△:さらさら感がやや感じられる
×:さらさら感が感じられない
「キメの細かさ」;◎:キメが充分感じられる
○:キメが感じられる
△:キメがやや感じられる
×:キメが感じられない
「手への貼り付き感のなさ」;◎:手への貼り付き感が全く感じられない
○:手への貼り付き感が感じられない
△:手への貼り付き感がやや感じられる
×:手への貼り付き感が感じられる
「木材の触感が感じられるか」;◎:木材の触感が非常に感じられる
○:木材の触感が感じられる
△:木材の触感がやや感じられる
×:木材の触感が感じられない “Smooth feeling”; ◎: Very smooth feeling ○: Feeling smooth feeling △: Feeling smooth feeling slightly: No feeling of smooth feeling “Fine texture”; ◎: Feeling enough Yes: Texture is felt Δ: Texture is slightly felt ×: Texture is not felt “No feeling of sticking to hand”; ◎: Feeling of sticking to hand is not felt at all ○: Feeling to hand A feeling of sticking is not felt. △: A feeling of sticking to the hand is felt slightly. X: A feeling of sticking to the hand is felt. “Can you feel the tactile feel of wood?”; ◎: The tactile feel of wood is very felt. ○: The feel of wood is felt △: The feel of wood is slightly felt ×: The feel of wood is not felt
得られた表面加飾用フィルムを以下の耐候試験に供した後、表面加飾層の表面粗さ(SMD)および静摩擦指標を再び測定し、初期の表面粗さ(SMD)または静摩擦指標から耐候試験後の表面粗さ(SMD)または静摩擦指標を差し引いた値(変化値)を求めるとともに、耐候試験後の表面加飾用フィルムについて上記初期触感評価と同様の方法で「さらさら感」を評価した。表面粗さ(SMD)の変化値は±0.1であれば許容範囲であり、静摩擦指標の変化値は±0.4であれば許容範囲である。
[耐候試験]
JIS K 5400(促進耐候性)に準じ、WEL-SUN-HCH B BR型サンシャインスーパーロングライフウェザーメーター(スガ試験機社製)を用い、照射温度63℃、湿度50%RH、120分周期中18分間降雨ありの条件にて200時間、試料とする表面加飾用フィルムへの照射を行った。照射後、試料を、23℃、50%RHの雰囲気で5時間以上風乾した。 (change over time)
The obtained surface decoration film was subjected to the following weather resistance test, and then the surface roughness (SMD) and static friction index of the surface decoration layer were measured again, and the weather resistance was determined from the initial surface roughness (SMD) or static friction index. The surface roughness after the test (SMD) or the value obtained by subtracting the static friction index (change value) was determined, and the “smooth feeling” was evaluated by the same method as the initial tactile sensation evaluation for the surface decoration film after the weather resistance test. . The change value of the surface roughness (SMD) is acceptable if it is ± 0.1, and the change value of the static friction index is acceptable if it is ± 0.4.
[Weather resistance test]
According to JIS K 5400 (accelerated weather resistance), WEL-SUN-HCH B BR type sunshine super long life weather meter (manufactured by Suga Test Instruments Co., Ltd.), irradiation temperature 63 ° C., humidity 50% RH, 18 in 120 minute period Irradiation was performed on the surface decorating film as a sample for 200 hours under conditions of rainfall for a minute. After irradiation, the sample was air-dried for 5 hours or more in an atmosphere of 23 ° C. and 50% RH.
Claims (8)
- 基材フィルム上に表面加飾層を備えた表面加飾用フィルムであって、
前記表面加飾層が、硬化性樹脂化合物の硬化物と、重量平均分子量が20,000~100,000である第4級アンモニウム塩タイプのカチオン系樹脂と、下記条件(i)~(iv)を満足する2種以上の無機系微粒子とを含有してなり、かつ前記表面加飾層は、KES表面試験機で測定される表面粗さSMDが0.40μm以上、2.0μm以下であることを特徴とするさらさら感に優れた表面加飾用フィルム。
(i)平均粒子径が1.0~50μmの範囲内にあること
(ii)平均粒子径がそれぞれ1.0μm以上異なっていること
(iii)最も平均粒子径の小さい粒子の平均粒子径が1.0μm以上16μm以下であること
(iv)最も平均粒子径の大きい粒子の平均粒子径が8μm以上50μm以下であること It is a film for surface decoration provided with a surface decoration layer on a substrate film,
The surface decoration layer includes 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 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 μm or more and 2.0 μm or less. A surface decorating film with an excellent feeling of smoothness.
(i) The average particle diameter is in the range of 1.0 to 50 μm.
(ii) The average particle diameter is different by 1.0 μm or more.
(iii) The average particle diameter of the smallest average particle diameter is 1.0 μm or more and 16 μm or less.
(iv) The average particle size of the largest average particle size is 8 μm or more and 50 μm or less. - 前記表面加飾層は、KES表面摩擦試験機でシリコンセンサー摩擦子を用いて測定される静摩擦指標が1.0~4.5である請求項1に記載の表面加飾用フィルム。 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 as measured with a KES surface friction tester using a silicon sensor friction element.
- 前記無機系微粒子の総含有量が、前記硬化性樹脂化合物の硬化物および前記カチオン系樹脂の合計100質量部に対して5~35質量部である請求項1または2に記載の表面加飾用フィルム。 The surface decoration according to claim 1 or 2, wherein the total content of the inorganic fine particles is 5 to 35 parts by mass with respect to a total of 100 parts by mass of the cured product of the curable resin compound and the cationic resin. the film.
- 2種以上含有される前記無機系微粒子のうち、最も平均粒子径の小さい粒子の、全無機系微粒子に対する含有量が15質量%以上85質量%以下である請求項1~3のいずれか1項に記載の表面加飾用フィルム。 The content of particles having the smallest average particle diameter among the two or more kinds of inorganic fine particles contained in the inorganic fine particles is 15% by mass or more and 85% by mass or less. The film for surface decoration as described in 2.
- 2種以上含有される前記無機系微粒子のうち、最も平均粒子径の大きい粒子の、全無機系微粒子に対する含有量が15質量%以上85質量%以下である請求項1~4のいずれか1項に記載の表面加飾用フィルム。 The content of particles having the largest average particle diameter among the two or more kinds of inorganic fine particles contained in the inorganic fine particles is 15% by mass or more and 85% by mass or less. The film for surface decoration as described in 2.
- 前記無機系微粒子1種当たりの含有量が、前記硬化性樹脂化合物の硬化物および前記カチオン系樹脂の合計100質量部に対して0.75~29.75質量部である請求項1~5のいずれか1項に記載の表面加飾用フィルム。 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 in total of the cured product of the curable resin compound and the cationic resin. The film for surface decoration of any one of Claims 1.
- 前記第4級アンモニウム塩タイプのカチオン系樹脂を、前記硬化性樹脂化合物の硬化物100質量部に対して2~25質量部含む請求項1~6のいずれか1項に記載の表面加飾用フィルム。 The surface decoration according to any one of claims 1 to 6, comprising 2 to 25 parts by mass of the quaternary ammonium salt type cationic resin with respect to 100 parts by mass of the cured product of the curable resin compound. the film.
- 前記硬化性樹脂化合物は、3官能以上の電離放射線硬化型樹脂化合物を5質量%以上含む請求項1~7のいずれか1項に記載の表面加飾用フィルム。 The surface-decorating film according to any one of claims 1 to 7, wherein the curable resin compound contains 5 mass% or more of a tri- or higher functional ionizing radiation curable resin compound.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020157017456A KR102180699B1 (en) | 2013-01-29 | 2014-01-27 | Film for surface decoration |
CN201480006628.0A CN104955644B (en) | 2013-01-29 | 2014-01-27 | Incrustation film |
JP2014517922A JP5620613B1 (en) | 2013-01-29 | 2014-01-27 | Surface decoration film |
Applications Claiming Priority (2)
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JP2013-014817 | 2013-01-29 | ||
JP2013014817 | 2013-01-29 |
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WO2014119511A1 true WO2014119511A1 (en) | 2014-08-07 |
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PCT/JP2014/051667 WO2014119511A1 (en) | 2013-01-29 | 2014-01-27 | Film for surface decoration |
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JP (1) | JP5620613B1 (en) |
KR (1) | KR102180699B1 (en) |
CN (1) | CN104955644B (en) |
TW (1) | TW201434641A (en) |
WO (1) | WO2014119511A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2018108699A (en) * | 2017-01-05 | 2018-07-12 | 凸版印刷株式会社 | Decorative sheet and decorative laminate |
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JP2001105541A (en) * | 1999-10-06 | 2001-04-17 | Dainippon Printing Co Ltd | Abrasion resistant decorative material |
JP2001232727A (en) * | 1999-12-15 | 2001-08-28 | Dainippon Printing Co Ltd | Decorative material having surface coating film layer |
JP2006281492A (en) * | 2005-03-31 | 2006-10-19 | Toppan Printing Co Ltd | Decorative material |
JP2007118596A (en) * | 2005-09-30 | 2007-05-17 | Dainippon Printing Co Ltd | Decorative sheet |
JP2012040700A (en) * | 2010-08-13 | 2012-03-01 | Nissha Printing Co Ltd | Decorative article with fingerprint-proof mat surface |
JP2012218284A (en) * | 2011-04-08 | 2012-11-12 | Toyobo Co Ltd | Surface decorative film having tattile impression of plain wood |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006145910A (en) * | 2004-11-19 | 2006-06-08 | Sekisui Chem Co Ltd | Noninflammable sheet for internal illumination signboard |
-
2014
- 2014-01-27 KR KR1020157017456A patent/KR102180699B1/en active IP Right Grant
- 2014-01-27 JP JP2014517922A patent/JP5620613B1/en active Active
- 2014-01-27 WO PCT/JP2014/051667 patent/WO2014119511A1/en active Application Filing
- 2014-01-27 CN CN201480006628.0A patent/CN104955644B/en active Active
- 2014-01-29 TW TW103103356A patent/TW201434641A/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001105541A (en) * | 1999-10-06 | 2001-04-17 | Dainippon Printing Co Ltd | Abrasion resistant decorative material |
JP2001232727A (en) * | 1999-12-15 | 2001-08-28 | Dainippon Printing Co Ltd | Decorative material having surface coating film layer |
JP2006281492A (en) * | 2005-03-31 | 2006-10-19 | Toppan Printing Co Ltd | Decorative material |
JP2007118596A (en) * | 2005-09-30 | 2007-05-17 | Dainippon Printing Co Ltd | Decorative sheet |
JP2012040700A (en) * | 2010-08-13 | 2012-03-01 | Nissha Printing Co Ltd | Decorative article with fingerprint-proof mat surface |
JP2012218284A (en) * | 2011-04-08 | 2012-11-12 | Toyobo Co Ltd | Surface decorative film having tattile impression of plain wood |
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JP2018108699A (en) * | 2017-01-05 | 2018-07-12 | 凸版印刷株式会社 | Decorative sheet and decorative laminate |
Also Published As
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JP5620613B1 (en) | 2014-11-05 |
JPWO2014119511A1 (en) | 2017-01-26 |
TW201434641A (en) | 2014-09-16 |
KR20150114462A (en) | 2015-10-12 |
CN104955644B (en) | 2017-03-15 |
CN104955644A (en) | 2015-09-30 |
KR102180699B1 (en) | 2020-11-20 |
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