WO2012128050A1 - 傷付き防止フィルム - Google Patents
傷付き防止フィルム Download PDFInfo
- Publication number
- WO2012128050A1 WO2012128050A1 PCT/JP2012/055871 JP2012055871W WO2012128050A1 WO 2012128050 A1 WO2012128050 A1 WO 2012128050A1 JP 2012055871 W JP2012055871 W JP 2012055871W WO 2012128050 A1 WO2012128050 A1 WO 2012128050A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- group
- vinyl compound
- monomer
- resistance
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the present invention relates to a film used as an alternative to directly applying a paint to an article for surface protection or decoration of the article.
- the present invention relates to a film used for surface protection and decoration of automobile exterior parts, wall materials, floor materials, white goods such as refrigerators.
- melamine is used in accordance with the material of the member.
- Direct coating of curable resin paints such as resin, isocyanate resin and urethane resin has been performed.
- hard coatings such as UV curable acrylic resins are directly applied to home appliance housings to provide functions such as scratch resistance, durability, contamination resistance, and design. I came.
- Patent Document 1 a film decorative material instead of direct coating of paint.
- This film cosmetic material solves problems such as workability, environmental safety, and designability in direct coating, but is insufficient in terms of scratch resistance, weather resistance, durability, stain resistance, and corrosion resistance. It is.
- Patent Document 2 a cured product of a polydimethylsiloxane copolymer in which polycaprolactone and polysiloxane are introduced into a skeleton has been proposed (Patent Document 2).
- Patent Document 2 a cured product of a polydimethylsiloxane copolymer in which polycaprolactone and polysiloxane are introduced into a skeleton has been proposed (Patent Document 2).
- the properties such as scratch resistance, weather resistance, durability, contamination resistance, corrosion resistance, bending resistance, curved surface followability, and impact resistance are still not sufficient.
- An object of the present invention is to provide a film that is useful as a means for replacing the direct coating of paint for surface protection and decoration of articles, and has excellent scratch resistance.
- the inventor of the present invention has a coating film comprising a cross-linked product of a composition comprising a vinyl compound copolymer and a polyisocyanate, and the monomer unit constituting the copolymer contains a vinyl compound having a specific carbon number.
- the present invention has been accomplished by finding that a coating film having particularly excellent scratch resistance (scratch resilience and scratch resistance against friction), low temperature impact resistance and stain resistance can be obtained.
- Scratch resilience means that when external pressure is applied to the coating surface, it immediately elastically deforms and does not easily break, and after the external pressure is removed, the deformation does not remain as plastic deformation. It means the nature of being.
- the film and laminated film of the present invention show excellent viscoelasticity because of the viscoelastic behavior of the Forked model, and have excellent scratch resistance against friction, as well as contamination resistance, weather resistance, chemical resistance, bending resistance and resistance to abrasion. Since it is excellent in impact property, it is useful as a scratch-preventing film or a decorative film, for example, as an alternative to the direct coating of paint on the surface of an article, for example, the surface of a wall surface, home appliance, automobile part or the like.
- the film of the present invention comprises a crosslinked product of a composition comprising a vinyl compound copolymer and polyisocyanate, and the vinyl compound copolymer contains the following monomer units (A) to (D).
- the monomer (A) is a vinyl compound having no siloxane structure and no hydroxyl group.
- Examples of the monomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydro (Meth) acrylic esters such as furfuryl (meth) acrylate, 2-stearyl (meth) acrylate and lauryl (meth) acrylate; alkyl such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether Vinyl ethers; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; cyano group-containing vinyl compounds such
- Examples thereof include carboxyl group-containing vinyl compounds; and amide group-containing vinyl compounds such as (meth) acrylamide. Of these, methyl (meth) acrylate, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferred.
- the monomer (B) is a vinyl compound having a polydimethylsiloxane structure and having no hydroxyl group.
- This vinyl compound (B) can impart lubricity to the film of the present invention, and as a result, can further enhance the scratch resistance of the film.
- a compound having a siloxane structure such as monomer (B)
- the monomer (B) is not in a free form but exists as a constituent component of the vinyl compound copolymer, so that the scratch resistance can be increased without causing a decrease in stain resistance. it can.
- the monomer (B) polydimethylsiloxane having an acrylic ester or methacrylic ester residue at one end is preferred because of the ease of polymerization reaction with other vinyl monomers.
- the monomer (B) preferably has a molecular weight of 1,000 to 30,000 from the viewpoint of imparting lubricity. When the molecular weight exceeds 30000, the effect of imparting lubricity is poor. Also, such high molecular weight monomers are difficult to synthesize.
- a commercially available monomer can be used as the monomer (B).
- X-22-2426 molecular weight: about 14000
- X-22-174DX molecular weight: about 5000
- AK-32 molecular weight: about 20000
- X-22-173DX molecular weight, manufactured by Shin-Etsu Chemical Co., Ltd.
- Polydimethylsiloxanes such as about 5000 single-ended epoxy-modified polydimethylsiloxanes) can also be introduced by known methods. *
- the monomer (C) is a vinyl compound having a linear or branched alkyl group having a hydroxyl group, and the alkyl group has 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
- Examples of the monomer (C) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate. Hydroxyethyl acrylamide, allyl alcohol and the like, among which acrylic acid 2-hydroxyethyl ester and methacrylic acid 2-hydroxyethyl ester are preferred.
- R is H or CH 3
- Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the end
- Y is optionally a ring-opening lactone group (—CO— (CH 2 ) n—O—, Where n is an integer from 4 to 6, carbonate group (—O—CO—O—), ester group (—CO—O—), ether group (—O—) and urethane group (—NH—CO).
- ring-opening lactone group and the like may have one or more groups selected from the group consisting of 40 to 120 carbon atoms.
- the carbon number of Y is a particularly important factor for scratch resistance. When the carbon number is less than 40, the resulting coating film is inferior in scratch resistance. Also, the impact resistance at low temperatures is poor. When the number of carbon atoms is more than 120, the stain resistance is poor.
- the carbon number is preferably 46 to 90.
- Monomer (D) is, for example, (meth) acrylic acid and a long-chain glycol having hydroxyl groups at both ends represented by the formula HO-Y, for example, a long-chain glycol having a molecular weight of 594 to 1714 (carbon number 40 to 120), And obtained by dehydration condensation.
- Y may have the ring-opening lactone group or the like as desired. Having such a group is preferable in terms of easy control of the carbon number of Y. More preferably, Y has a polylactone structure and / or a polycarbonate structure. When Y is branched, a ring-opening lactone group or the like is preferably present in the main chain rather than in the side chain. In addition, when Y has a ring-opening lactone group or the like, the carbon number of Y includes the number of carbons contained in the ring-opening lactone group or the like.
- the monomer (D) in which Y has a ring-opening lactone group can be obtained, for example, by dehydration condensation between (meth) acrylic acid and polycaprolactone diol.
- the dehydration condensation can be carried out according to a known method, for example, by heating and refluxing with an acid catalyst such as p-toluenesulfonic acid and a polymerization inhibitor such as hydroquinone or methylhydroquinone in an organic solvent such as benzene or toluene.
- an acid catalyst such as p-toluenesulfonic acid
- a polymerization inhibitor such as hydroquinone or methylhydroquinone in an organic solvent such as benzene or toluene.
- Examples of the polycaprolactone diol include Plaxel 210 (carbon number 50) and Plaxel 220 (carbon number 104) manufactured by Daicel Chemical Industries, Ltd.
- the monomer (D) in which Y has a polycarbonate structure can be produced by dehydration condensation between (meth) acrylic acid and polycarbonate diol.
- the polycarbonate diol include Plaxel CD210 (carbon number 48) and Plaxel CD220 (carbon number 97) manufactured by Daicel Chemical Industries, Ltd.
- the vinyl compound copolymer in the present invention is obtained by copolymerization of the monomers (A) to (D).
- Formula (1) shows the relationship between the molar amounts of the monomers (A) and (B) having no hydroxyl group, and the molar amount of the monomer (B) is the total molar amount of the monomer (A) and the monomer (B). It means 5% or less.
- the amount of the monomer (B) is larger than this, the stain resistance may be lowered.
- the lower limit depends on the content of the polydimethylsiloxane structure of the monomer (B) used, but in order to obtain the effect of imparting lubricity to the film of the present invention, the total molar amount of the monomer (A) and the monomer (B) It is preferable that it is 0.5% or more.
- Formula (3) shows the relationship between the molar amounts of the monomers (C) and (D) having a hydroxyl group.
- 4d / 3> c that is, when the amount of the monomer (C) is too small or the amount of the monomer (D) is too large, the crosslinking density becomes too low, and the stain resistance, heat resistance, weather resistance and chemical resistance are too low. Sex is reduced. In addition, the scratch resistance may be reduced.
- c> 40d that is, when the amount of the monomer (C) is too large or the amount of the monomer (D) is too small, the crosslink density becomes too high, and a rigid and glass-like cured film is provided, so that the scratch recovery property is obtained. No longer develops.
- bending resistance and impact resistance may be reduced.
- c and d satisfy 8d / 5 ⁇ c ⁇ 8d, more preferably 2d ⁇ c ⁇ 4d.
- the vinyl compound copolymer is usually produced by solution polymerization.
- Solvents used in solution polymerization include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate, and ethanol And alcohol solvents such as isopropanol, butanol, and isobutanol, and the like can be used alone or as a mixed solvent of two or more.
- polymerization initiators such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, and azobisisobutyronitrile can also be used.
- the polymerization temperature is preferably 60 to 160 ° C., and the reaction time is preferably 5 to 15 hours.
- the resulting vinyl compound copolymer is then mixed with polyisocyanate, and the resulting mixed paint is applied to the surface of the thermoplastic resin film and crosslinked at room temperature or by heating to obtain the laminated film of the present invention. be able to.
- the film of this invention is obtained by peeling a thermoplastic resin film from the said laminated
- a well-known web coating method can be used. Specific examples include roll coat, gravure coat, reverse coat, roll brush, spray coat, air knife coat and die coat.
- the thickness of the resulting coating film is preferably 10 to 100 ⁇ m after drying and curing. If the film is too thin, the resulting film of the present invention may not exhibit the ability to restore scratches. If the film is too thick, there may be a problem that the paint flows during application, or the cost increases unnecessarily.
- the polyisocyanate is a compound having a —N ⁇ C ⁇ O structure in the molecule.
- methylene bis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane of hexamethylene diisocyanate Polyisocyanates such as adducts, trimethylolpropane adducts of isophorone diisocyanate, isocyanurates of tolylene diisocyanate, isocyanurates of hexamethylene diisocyanate, isocyanurates of isophorone diisocyanate and biurets of hexamethylene diisocyanate, or the above polyisocyanates And urethane crosslinking agents such as block type isocyanates.
- methylene bis-4-cyclohexyl isocyanate trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate and biuret of hexamethylene diisocyanate And the like.
- a catalyst such as dibutyltin dilaurate and dibutyltin diethylhexoate may be added as necessary.
- the amount of the polyisocyanate is preferably 1: 0.7 to 1: 1.4, more preferably 1: ratio of the number of moles of hydroxyl groups in the vinyl compound copolymer to the number of moles of isocyanate groups in the polyisocyanate.
- the amount is from 0.9 to 1: 1.2. If the amount of isocyanate is too small, the stain resistance and weather resistance may decrease. On the other hand, if the amount of isocyanate is too large, the scratch recovery property and the bending resistance may deteriorate.
- Crosslinking can be performed by room temperature drying or heat drying.
- room temperature drying can be performed over 6 hours to 1 week. Heating and drying can be performed at 40 to 300 ° C. for 5 seconds to 120 minutes.
- the drying temperature and time are selected as appropriate in accordance with the properties of the thermoplastic resin film to which the mixed paint is applied, and in some cases, heating drying and room temperature drying may be combined.
- the thermoplastic resin film may be softened during the drying process, resulting in problems such as tearing, wrinkling, and shrinkage.
- a method of applying and drying the mixed paint after fixing the thermoplastic resin film on a support such as metal, glass, earthenware, thermosetting resin, or thermoplastic resin with a high softening point in advance. It can be selected appropriately.
- thermoplastic resin film to which the paint is applied examples include, for example, polyvinyl chloride resin, non-crystalline, low-crystalline or crystalline polyester, polyolefin such as polypropylene and polyethylene, acrylonitrile / butadiene / styrene copolymer resin, and the like.
- ABS resin acrylonitrile / butadiene / styrene copolymer resin
- thermoplastic resins such as polyamide, acrylic, polycarbonate, polyurethane, etc., unstretched film, uniaxially stretched Includes films and biaxially oriented films.
- a non-stretched film of a polyvinyl chloride resin or an amorphous polyester resin, or a stretched crystalline polyester film is particularly preferred.
- the film of the present invention is obtained by peeling the thermoplastic resin film from the laminated film obtained by applying the paint to the thermoplastic resin film, the coated surface of the thermoplastic resin film is subjected to a release treatment in advance. Is preferred.
- the thickness of the thermoplastic resin film is not particularly limited, but is usually 20 to 500 ⁇ m, and is preferably 75 in consideration of application to vacuum forming, membrane press forming, pressure press forming, in-mold forming, or insert forming described later. ⁇ 300 ⁇ m.
- the coating film is elastically deformed.
- embossing may be difficult, but the embossing has a coating thickness of 10 to 30 ⁇ m, a thermoplastic resin film thickness of 80 to 300 ⁇ m, and a surface roughness Rz of 20 ⁇ m or more. A good embossed shape can be obtained by pressing with a roll.
- the film and laminated film of the present invention are excellent in scratch recovery properties and stain resistance, and are excellent in weather resistance, chemical resistance, bending resistance and impact resistance.
- it is useful as an anti-scratch film or a decorative film.
- it can be suitably used for the surfaces of automobile parts such as door sashes, moldings, fenders, bumpers, etc., housings and information display parts of home appliances, building wall materials and flooring materials, and furniture products.
- the film or laminated film of the present invention When the film or laminated film of the present invention is used by being attached to a planar member such as a wall material, flooring, image graphics, and automobile door sash, for example, one side of the film of the present invention or the laminated film of the present invention.
- a pressure-sensitive adhesive layer or an adhesive layer can be provided on the thermoplastic resin film of the film, and cut into a desired shape and attached.
- sticking in order to prevent air from being taken in between the film or laminated film of the present invention and the member to cause swelling and spoil the appearance, there is no air leakage on the surface of the pressure-sensitive adhesive layer or adhesive layer. It is preferable to provide a groove for this purpose.
- the design of the air groove is
- the width of the groove is preferably 10 to 200 ⁇ m, more preferably 50 to 150 ⁇ m.
- the depth of the groove is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m, and its cross-sectional shape is semicircular.
- the pressure-sensitive adhesive layer separated by the grooves when the surface of the pressure-sensitive adhesive layer having the grooves is viewed from the vertical direction is a regular triangle, regular square, rhombus or regular hexagon. It is recommended that the grooves be arranged so as to have a repeating structure.
- the film or laminated film of the present invention when used for surface protection or decoration of a member having a three-dimensional and complicated shape such as a housing of a home appliance, an automobile instrument panel, a shift knob, an assist grip, etc. , Vacuum molding, membrane press molding, pressure press molding, in-mold molding, insert molding, and the like can be integrally formed.
- a member provided with an adhesive layer or an adhesive layer on one side of the film of the present invention or the thermoplastic resin film of the laminated film of the present invention is integrated with the above member.
- the glass transition point of the thermoplastic resin film is preferably 60 to 130 ° C.
- acrylic resin, polyvinyl chloride Resin, polyester resin and acrylonitrile / butadiene / styrene copolymer resin films are preferred.
- the isocyanate group of the polyisocyanate should be 0.7 to 1.2 equivalents relative to 1 equivalent of the hydroxyl group of the vinyl compound copolymer. Is preferred.
- Example 1 Under a nitrogen atmosphere, 100 parts by mass of methyl isobutyl ketone was placed in a 500 ml flask and heated to 100 ° C. Further, a total of 100 parts by mass of the monomers (A) to (D) in mol% shown in Table 1 (that is, 14 parts by mass of monomer (A), 15 parts by mass of monomer (B), 15 parts by mass of monomer (C) and monomer (D) 57 parts by mass) and 1 part by mass of 2,2′-azobisisobutyronitrile (manufactured by Nippon Finechem Co., Ltd., ABN-R) were mixed, and the mixture was added to methyl isobutyl ketone at 100 ° C. for 3 hours. It was dripped over. The mixture was further refluxed for 6 hours to obtain the desired copolymer (solid content 50%).
- Table 1 that is, 14 parts by mass of monomer (A), 15 parts by mass of monomer (B), 15 parts by mass of monomer (
- a paint obtained by mixing 100 parts by mass of the obtained vinyl compound copolymer with 34 parts by mass of polyisocyanate was used as a release treatment surface of a polyester film “Therapyl 38” (trade name) manufactured by Toray Film Processing Co., Ltd. After coating the coating film thickness to 50 ⁇ m after drying, the coating film was heated at 150 ° C. for 30 minutes and then allowed to stand at room temperature for 24 hours to form a coating film. This coating film was peeled off from the therapy 38, and the target film (i) was obtained. The following tests (1) to (13) were performed on the obtained film. The results are shown in Table 1.
- Examples 2 to 19 and Comparative Examples 1 to 9 Using each monomer shown in Table 1 in the amount of mol% shown in Table 1 (the number in parentheses is part by mass), 100 parts by mass of the vinyl compound copolymer obtained by copolymerization in the same manner as in Example 1 was used.
- the coating thickness obtained by mixing the polyisocyanate in the amount (parts by mass) shown in Table 1 with a coating film thickness after drying on one side of a polyester film “Embret S50” (trade name) manufactured by Unitika Ltd. is 20 ⁇ m. After coating, the film was heated at 150 ° C. for 30 minutes, and further allowed to stand at room temperature for 24 hours to form a coating film, whereby the desired laminated film (B) was obtained.
- Example 19 25 parts by mass of polydimethylsiloxane was mixed with 100 parts by mass of the vinyl compound copolymer and 34 parts by mass of polyisocyanate to obtain a paint.
- the following tests (1) to (15) were performed on the obtained laminated film. The results are shown in Table 1.
- Placelel FM2D (caprolactone 2 mol adduct of hydroxyethyl methacrylate, molecular weight 358) manufactured by Daicel Chemical Industries, Ltd. and adipic acid (molecular weight 146) were subjected to dehydration condensation using an acid catalyst.
- Placelel 205 (caprolactone tetramer diol, H— ⁇ O— (CH 2 ) 5 —CO ⁇ 2 —O—CH 2 —O—CH, manufactured by Daicel Chemical Industries, Ltd., was added to the terminal carboxylic acid-modified methacrylate.
- the film (A) or the laminated film (B) obtained above was cut into a length of 150 mm and a width of 75 mm to obtain a test piece, which was placed on a glass plate.
- the laminated film (b) it was placed so that the coating surface was the surface.
- a four-row brass brush (load 500 gf) manufactured by Nakaya Brush Industry rubbing the surface of the test piece 10 times at a distance of 100 mm one way, and then removing the brass brush quickly until the scratches on the surface disappear. Time was observed.
- ⁇ The scratches disappeared within 1 minute.
- X The scratch did not disappear even after 24 hours.
- the coating film (a) or the laminated film (b) is cut out to 100 ⁇ 25 mm and attached to an A & D Tensilon RTG-1310 tensile tester with a distance between chucks of 50 mm, at a tensile speed of 200 mm / min.
- the 10% modulus value when the tensile test was performed was measured. The smaller this value is, the more likely it is torn during handling and the poorer the handling.
- 10% modulus value is 1 N / 25 mm or more and less than 10 N / 25 mm
- 10% modulus value is less than 1 N / 25 mm
- the coating film and laminated film of the present invention are excellent in scratch resistance, and are also excellent in stain resistance, weather resistance, chemical resistance, bending resistance and impact resistance.
- Comparative Example 1 which does not satisfy the formula (2) and the total amount of the monomer (A) and the monomer (B) is too large is inferior in scratch resistance, chemical resistance, weather resistance and stain resistance, and the monomer (A In Comparative Example 2 in which the total molar amount of the monomer (B) is too small, the scratch resistance and low temperature impact resistance were poor.
- Comparative Example 3 which does not satisfy Formula (3) and the amount of monomer (C) is too large, the scratch resistance, bending resistance and impact resistance are inferior, and in Comparative Example 4 where the amount of monomer (C) is too small, Inferior in scratch resistance and stain resistance.
- Example 20 100 parts by mass of a vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., degree of polymerization 1100), 20 parts by mass of a polyester plasticizer ⁇ manufactured by Kao Corporation, HA-5 (trade name) ⁇ and carbon black (manufactured by Mitsubishi Chemical Corporation, A composition of 5 parts by mass of MCF # 1000 (trade name) was formed by a calendering machine to obtain a base film (thickness: 100 ⁇ m). A film obtained in the same manner as in Example 1 except that the thickness of the coating film was 15 ⁇ m was bonded to one surface of the base film with a metal roll to obtain a laminated film. Next, an embossed film 1 was obtained by pressing a satin embossing roll having a surface roughness Rz of 30 ⁇ m at 100 ° C. and 5 kgf / cm 2 on the surface of the coating film.
- a satin embossing roll having a surface roughness Rz of 30 ⁇ m
- Example 21 Embossed film 2 was obtained in the same manner as in Example 20 except that the coating film thickness was changed to 25 ⁇ m in Example 20.
- Example 22 Embossed film 3 was obtained in the same manner as in Example 20 except that the thickness of the base film was changed to 250 ⁇ m in Example 20.
- Example 23 the base film was composed of 100 parts by mass of PET-G resin (Easterman Chemical Co., Easter G6763) and 5 parts by mass of carbon black (Mitsubishi Chemical Co., Ltd., MCF # 1000 (trade name)).
- An embossed film 4 was obtained in the same manner as in Example 20, except that the product was manufactured using an extrusion die molding machine (thickness: 100 ⁇ m).
- Example 20 an embossed film 5 was obtained in the same manner as in Example 20 except that the surface roughness Rz of the embossing roll was 10 ⁇ m.
- Reference example 2 Embossed film 6 was obtained in the same manner as in Example 20 except that the coating film thickness in Example 20 was changed to 5 ⁇ m.
- Reference example 3 Embossed film 7 was obtained in the same manner as in Example 20 except that the coating film thickness was 40 ⁇ m in Example 20.
- Example 20 except that 100 parts by weight of ALLEX26 K-37 (trade name) made by Nippon Kaiko Paint Co., Ltd. and 10 parts by weight of ALLEX26 curing agent were used as the coating material for the coating film, which does not have scratch restoring properties. In the same manner, an embossed film 8 was obtained.
- ALLEX26 K-37 trade name
- ALLEX26 curing agent 10 parts by weight
- the embossed films 1 to 8 obtained above were subjected to the following embossability test and the above tests (1) and (14). The results are shown in Table 2.
- Embossability The coating surface of the obtained embossed film was visually evaluated according to the following evaluation criteria. ⁇ : Embossing is formed over the entire surface of the coating film, and there is no cracking or perforation of the coating film. X: Little or no embossing is formed, or there are cracks and holes in the coating film.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
(A)シロキサン構造および水酸基を有しないビニル化合物(aモル%)、
(B)ポリジメチルシロキサン構造を有しかつ水酸基を有しないビニル化合物(bモル%)、
(C)水酸基を有する直鎖状または分岐状のアルキル基を有し、該アルキル基の炭素数が1~6であるビニル化合物(cモル%)、および
(D)下記式:
CH2=C(R)-COO-Y
[ここで、RはHまたはCH3であり、Yは末端に水酸基を有する直鎖状または分岐状飽和炭化水素基であり、Yは所望により開環ラクトン基(-CO-(CH2)n-O-、ここでnは4~6の整数である)、カーボネート基(-O-CO-O-)、エステル基(-CO-O-)、エーテル基(-O-)およびウレタン基(-NH-CO-O-)から成る群から選択される1以上の基を有していてもよく、かつ40~120の炭素原子を有する]を有するビニル化合物(dモル%)、
を含み、上記a~dが、a+b+c+d=100でありかつ下記式(1)~(3):
0<{b/(a+b)}x100≦5・・・(1)
3(c+d)/4≦(a+b)≦4(c+d) ・・・(2)
4d/3≦c≦40d ・・・(3)
を満たすところのフィルムである。
また、本発明は、熱可塑性樹脂フィルムの少なくとも片面に上記フィルムを有する積層フィルムも提供する。
モノマー(A)は、シロキサン構造および水酸基を有しないビニル化合物である。モノマー(A)としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、2-ステアリル(メタ)アクリレートおよびラウリル(メタ)アクリレート等の(メタ)アクリル酸エステル;メチルビニルエーテル、エチルビニルエーテル、n-プロピルビニルエーテル、n-ブチルビニルエーテルおよびイソブチルビニルエーテル等のアルキルビニルエーテル;スチレンおよびα-メチルスチレン等の芳香族ビニル化合物;アクリロニトリルおよびメタクリロニトリル等のシアノ基含有ビニル化合物;酢酸ビニル等のカルボン酸ビニルエステル;塩化ビニル、塩化ビニリデン、弗化ビニルおよび弗化ビニリデン等のハロゲン元素含有ビニル化合物;グリシジル(メタ)アクリレートおよびアリルグリシジルエーテル等のエポキシ基含有ビニル化合物;アクリル酸およびメタクリル酸等のカルボキシル基含有ビニル化合物;および(メタ)アクリルアミド等のアミド基含有ビニル化合物などを挙げることができる。中でも、メチル(メタ)アクリレート、エチル(メタ)アクリレートおよびn-ブチル(メタ)アクリレートが好ましい。
モノマー(B)は、ポリジメチルシロキサン構造を有しかつ水酸基を有しないビニル化合物である。このビニル化合物(B)は、本発明のフィルムに潤滑性を与え、その結果、フィルムの耐擦傷性をより高めることができる。一般に、モノマー(B)のようにシロキサン構造を有する化合物は、遊離形で塗料組成物中に存在すると、組成物中の他の成分との相溶性や混和性が低い故にブリードアウトし、耐汚染性の低下をもたらすが、本発明では、モノマー(B)が遊離形ではなく、ビニル化合物共重合体の構成成分として存在するので、耐汚染性の低下を生じることなく耐擦傷性を高めることができる。
モノマー(C)は、水酸基を有する直鎖状または分岐状のアルキル基を有するビニル化合物であり、該アルキル基の炭素数が1~6、好ましくは2~4である。モノマー(C)としては、例えば、アクリル酸2-ヒドロキシエチル、メタクリル酸2-ヒドロキシエチル、アクリル酸2-ヒドロキシプロピル、メタクリル酸2-ヒドロキシプロピル、アクリル酸4-ヒドロキシブチル、メタクリル酸4-ヒドロキシブチル、ヒドロキシエチルアクリルアミド、アリルアルコール等が挙げられ、中でも、アクリル酸2-ヒドロキシエチルエステルおよびメタクリル酸2-ヒドロキシエチルエステルが好ましい。
モノマー(D)は、下記式:
CH2=C(R)-COO-Y
有するビニル化合物である。RはHまたはCH3であり、Yは末端に水酸基を有する直鎖状または分岐状飽和炭化水素基であり、Yは所望により開環ラクトン基(-CO-(CH2)n-O-、ここでnは4~6の整数である)、カーボネート基(-O-CO-O-)、エステル基(-CO-O-)、エーテル基(-O-)およびウレタン基(-NH-CO-O-)(以降、「開環ラクトン基等」と言うことがある)から成る群から選択される1以上の基を有していてもよく、かつ40~120の炭素原子を有する。Yの上記炭素数は、耐擦傷性のための特に重要な因子であり、上記炭素数が40未満であると、得られる塗膜の耐擦傷性に劣る。また、低温での耐衝撃性にも劣る。上記炭素数が120より多いと耐汚染性に劣る。上記炭素数は、好ましくは46~90である。
0<{b/(a+b)}x100≦5・・・(1)
3(c+d)/4≦(a+b)≦4(c+d) ・・・(2)
4d/3 ≦c≦40d ・・・(3)
窒素雰囲気下で、500ml容のフラスコにメチルイソブチルケトン100質量部を入れ、100℃に昇温した。また、表1に示すモル%のモノマー(A)~(D)の合計100質量部(すなわち、モノマー(A)14質量部、モノマー(B)15質量部、モノマー(C)15質量部およびモノマー(D)57質量部)および2,2'-アゾビスイソブチロニトリル(株式会社日本ファインケム製、ABN-R )1質量部を混合し、この混合物を100℃のメチルイソブチルケトン中に3時間かけて滴下した。更に6時間かけて加熱還流を行い、目的の共重合体(固形分50%)を得た。
表1に示す各モノマーを表1に示すモル%の量(括弧内の数字は質量部)で使用し、実施例1と同様に共重合して得られたビニル化合物共重合体100質量部を表1に示す量(質量部)のポリイソシアネートと混合して得た塗料を、ユニチカ(株)製のポリエステルフィルム「エンブレットS50」(商品名)の片面に乾燥後の塗膜厚みが20μmとなるように塗布した後、150℃で30分加熱し、更に室温で24時間放置して塗膜を形成し、目的の積層フィルム(ロ)を得た。なお、実施例19では、ビニル化合物共重合体100質量部およびポリイソシアネート34質量部とともにポリジメチルシロキサン25質量部を混合して塗料を得た。得られた積層フィルムについて下記試験(1)~(15)を行った。結果を表1に示す。
モノマー(A):三菱レイヨン株式会社製、メチルメタクリレート
モノマー(B):信越化学工業株式会社製のX-22-2426、片末端メタクリル変性ポリジメチルシロキサン、分子量:約14000
モノマー(C):株式会社日本触媒製、2-ヒドロキシエチルメタクリレート、水酸基含有アルキル基の炭素数2
モノマー(D-1):ダイセル化学工業株式会社製のプラクセルFA10L、ヒドロキシエチルアクリレートのカプロラクトン10mol付加物、Yの炭素数62、分子量1256
モノマー(D-2):下記方法で調製された化合物、Yの炭素数46、分子量1002
モノマー(D-3):下記方法で調製された化合物、Yの炭素数52、分子量1116
モノマー(D-4):下記方法で調製された化合物、Yの炭素数40、分子量888
モノマー(D-5):ダイセル化学工業株式会社製のプラクセルCD210(ポリカーボネートジオール、HO-(C6H12-O-CO-O)6-C6H12-OH)とアクリル酸の脱水縮合物、Yの炭素数48、分子量1036
モノマー(D-6):ダイセル化学工業株式会社製のプラクセルCD220(ポリカーボネートジオール、HO-(C6H12-O-CO-O)13-C6H12-OH)とアクリル酸の脱水縮合物、Yの炭素数97、分子量2044
比較モノマー(D-7):ダイセル化学工業株式会社製のプラクセルFM5、ヒドロキシエチルメタクリレートのカプロラクトン5mol付加物、Yの炭素数32、分子量700
比較モノマー(D-8):ダイセル化学工業株式会社製のプラクセルFM3、ヒドロキシエチルメタクリレートのカプロラクトン3mol付加物、Yの炭素数20、分子量472
比較モノマー(D-9):ダイセル化学工業株式会社製のプラクセル230(ポリカプロラクトンジオール、炭素数158)とアクリル酸の脱水縮合物、Yの炭素数158、分子量3096
ポリイソシアネート:日本ポリウレタン工業製のコロネートHX、固形分100%、NCO含量21.3質量%
ポリジメチルシロキサン:信越化学工業株式会社製のポリジメチルシロキサン、粘度100万CS
ダイセル化学工業株式会社製のプラクセルFM2D(ヒドロキシエチルメタクリレートのカプロラクトン2mol付加物、分子量358)とアジピン酸(分子量146)とを酸触媒を用いて脱水縮合を行って末端カルボン酸変性メタクリレートを合成した。続いて、この末端カルボン酸変性メタクリレートにダイセル化学工業株式会社製のプラクセル205(カプロラクトン4量体のジオール、H-{O-(CH2)5-CO}2-O-CH2-O-CH2-O-{CO-(CH2)5-O}2-H、分子量534)を加え、酸触媒を用いて脱水縮合を行って末端水酸基含有メタクリレートモノマー(D-2)を得た。
上記モノマー(D-2)の調製において、プラクセルFM2Dに代えて、ダイセル化学工業株式会社製のプラクセルFM3(ヒドロキシエチルメタクリレートのカプロラクトン3mol付加物、分子量472)を使用したこと以外は上記調製と同様にしてモノマー(D-3)を得た。
上記モノマー(D-2)の調製において、プラクセルFM2Dに代えて、ダイセル化学工業株式会社製のプラクセルFM1D(ヒドロキシエチルメタクリレートのカプロラクトン1mol付加物、分子量244)を使用したこと以外は上記調製と同様にしてモノマー(D-4)を得た。
(1)擦傷復元性
上記で得られたフィルム(イ)または積層フィルム(ロ)を長さ150mm×幅75mmに切り出して試験片とし、これを硝子板上に置いた。積層フィルム(ロ)の場合には塗膜面が表面になるように置いた。仲屋ブラシ工業製の4行真鍮ブラシ(荷重500gf)を用いて、試験片の表面を片道100mmの距離で10往復擦った後、真鍮ブラシを速やかに除去して表面についた擦傷が消失するまでの時間を観察した。
○:1分以内に擦傷が消失した。
△:1分超~24時間以内に擦傷が消失した。
×:24時間以上経過しても擦傷が消失しなかった。
上記で得られたフィルム(イ)または積層フィルム(ロ)を長さ200mm×幅25mmに切り出して試験片とし、これをJIS L 0849の学振試験機に置いた。積層フィルム(ロ)の場合には塗膜面が表面になるように置いた。続いて、学振試験機の摩擦端子に金巾3号を5重となる様に取り付けた後、500gf荷重を載せて試験片表面を200往復した後の表面の擦り傷の程度を確認した。
◎:擦り傷が見られなかった。
○:塗膜表面に10本未満の軽微な擦り傷が見られた。
△:塗膜表面に10本以上の軽微な擦り傷が見られた。
×:塗膜表面全体に明瞭な擦り傷が見られた。
上記で得られたフィルム(イ)または積層フィルム(ロ)を100mm×50mmの大きさに切り出し、日東電工製の両面テープNo.500Aを用いて厚さ0.3mmのアルミ板に貼り付けて試験片とした。積層フィルム(ロ)の場合には塗膜面が表面になるように貼り付けた。この試験片を、直径2mmのマンドレルを取り付けたJIS K 5600-5-1タイプ1の折り曲げ試験装置を用いて、塗膜面が外側になる様に2秒をかけて均等な速度で180°に折り曲げた。折り曲げ終了後、折り曲げた箇所の中央30mm部分について塗膜の割れの有無を確認した。
○:割れが生じなかった。
△:割れは生じないが、曲げた部分が白っぽくなった。
×:割れが生じた。
上記で得られたフィルム(イ)または積層フィルム(ロ)を100mm×50mmの大きさに切り出し、日東電工製の両面テープNo.500Aを用いて150mm×75mm×1mmのアルミ板に貼り付けて試験片とした。積層フィルム(ロ)の場合には塗膜面が表面になるように貼り付けた。この試験片を、JIS K 5600-5-3に基づいてφ1/4インチの鉄球を取り付けたデュポン式衝撃試験機に塗膜面が上になるように置き、荷重300gfの重りを20cmの高さから落下させて衝撃を与えた後に塗膜の割れの有無を評価した。
○:割れが生じなかった。
×:割れが生じた。
上記試験(4)と同様の試験を-10℃の雰囲気温度で行った。なお、試験片をデュポン式衝撃試験機に設置した後に5分経過して温度が一定となった状態で試験を実施した。
○:割れが生じなかった。
×:割れが生じた。
上記試験(4)と同様の試験片を用い、これを40℃の温水に168時間浸漬した後に取り出し、1時間以内に塗膜の外観を、以下の基準にしたがって目視評価した。
○:変化が見られなかった。
△:肉眼では確認できないが顕微鏡を使用すると確認できる程度の非常に小さい膨れ、剥れまたは割れがあり、それらに起因する僅かな光沢低下や染みが肉眼で確認された。
×:膨れ、剥れまたは割れが肉眼で確認された。
上記試験(4)と同様の試験片を用い、これを50℃、95%RHの恒温恒湿槽に168時間放置した後に取り出し、1時間以内に塗膜の外観を、試験(6)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を用い、これを100℃のギヤオーブンに1時間放置した後に取り出し、更に室温で1時間以上放置した後、塗膜の外観を、試験(4)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を用い、これに10%希硫酸2mlを滴下して室温で24時間放置した後、十分に水洗した。この試験片を更に室温で1時間以上放置した後、塗膜の外観を、試験(6)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を用い、これに5%炭酸ナトリウム水溶液2mlを滴下して40℃で6時間放置した後、十分に水洗した。この試験片を更に室温で1時間以上放置した後、塗膜の外観を、試験(6)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を用い、これにJIS K 2202に準拠する1号ガソリン2mlを滴下して室温で24時間放置した後、十分に水洗した。この試験片を更に室温で2時間以上放置した後、塗膜の外観を、試験(6)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を用い、これにエタノール2mlを滴下して室温で24時間放置した後、十分に水洗した。この試験片を更に室温で24時間以上放置した後、塗膜の外観を、試験(6)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を用い、これをサンシャインウェザオメーターで2000時間暴露した後、十分に水洗した。この試験片を更に室温で24時間以上放置した後、塗膜の外観を、試験(6)と同様の評価基準にしたがって目視評価した。
上記試験(4)と同様の試験片を3個用意し、これらをそれぞれ屋外に80、160および240日間放置した後、十分に水洗した。これらの試験片を更に室温で24時間以上放置した後、塗膜の外観を、下記の評価基準にしたがって目視評価した。
◎:いずれの試験片も外観の変化が見られなかった。
〇:240日間放置した試験片のみに、光沢低下、膨れまたは剥れなどが確認された。
△:80日間放置した試験片については変化が見られなかったが、他の2つの試験片については、光沢低下、膨れまたは剥れなどが確認された。
×:いずれの試験片にも、光沢低下、膨れまたは剥れなどが確認された。
塗膜(イ)または積層フィルム(ロ)を100×25mmに切り抜き、これをA&D製テンシロンRTG-1310引張試験機にチャック間距離を50mmにして取り付け、引張速度200mm/minで引張試験を行った時の10%モジュラス値を測定した。この値が小さいほど、取扱中に破れる可能性が高く、取扱性に劣る。
○:10%モジュラス値が10N/25mm以上
△:10%モジュラス値が1N/25mm以上かつ10N/25mm未満
×:10%モジュラス値が1N/25mm未満
塩化ビニル樹脂(信越化学工業株式会社製、重合度1100)100質量部、ポリエステル系可塑剤{花王株式会社製、HA-5(商品名)}20質量部およびカーボンブラック(三菱化学株式会社製、MCF#1000(商品名))5質量部の組成物をカレンダー成形機により製膜し、基材フィルム(厚み100μm)を得た。この基材フィルムの一方の面に、塗膜厚みが15μmであること以外は実施例1と同様にして得られたフィルムを金属ロールにより貼り合せて積層フィルムを得た。次いで、この塗膜表面に、表面粗度Rzが30μmの梨地エンボスロールを100℃、5kgf/cm2で押圧加工する事により、エンボス加工フィルム1を得た。
実施例20において塗膜厚みを25μmにした以外は実施例20と同様にして、エンボス加工フィルム2を得た。
実施例20において基材フィルムの厚みを250μmにした以外は実施例20と同様にして、エンボス加工フィルム3を得た。
実施例20において基材フィルムを、PET-G樹脂(イーストマンケミカル株式会社製、イースターG6763)100質量部およびカーボンブラック(三菱化学株式会社製、MCF#1000(商品名))5質量部の組成物を用いて押出ダイ成形機により製造した(厚み100μm)こと以外は実施例20と同様にして、エンボス加工フィルム4を得た。
実施例20においてエンボスロールの表面粗度Rzを10μmにした以外は実施例20と同様にして、エンボス加工フィルム5を得た。
実施例20において塗膜厚みを5μmにした以外は実施例20と同様にして、エンボス加工フィルム6を得た。
実施例20において塗膜厚みを40μmにした以外は実施例20と同様にして、エンボス加工フィルム7を得た。
塗膜のための塗料として、擦傷復元性を有しない、日本化工塗料株式会社製ALLEX26 K-37(商品名)100重量部とALLEX26硬化剤10重量部との塗料を使用した以外は実施例20と同様にして、エンボス加工フィルム8を得た。
得られたエンボス加工フィルムの塗膜表面を下記の評価基準にしたがって目視評価した。
○:エンボスが塗膜表面全体にわたって形成されており、塗膜の割れや穴開きもない。
×:エンボスがほとんどまたは全く形成されておらず、あるいは塗膜に割れや穴開きがある。
Claims (5)
- ビニル化合物共重合体およびポリイソシアネートからなる組成物の架橋物からなるフィルムにおいて、該ビニル化合物共重合体が、下記モノマー単位:
(A)シロキサン構造および水酸基を有しないビニル化合物(aモル%)、
(B)ポリジメチルシロキサン構造を有しかつ水酸基を有しないビニル化合物(bモル%)、
(C)水酸基を有する直鎖状または分岐状のアルキル基を有し、該アルキル基の炭素数が1~6であるビニル化合物(cモル%)、および
(D)下記式:
CH2=C(R)-COO-Y
[ここで、RはHまたはCH3であり、Yは末端に水酸基を有する直鎖状または分岐状飽和炭化水素基であり、Yは所望により開環ラクトン基(-CO-(CH2)n-O-、ここでnは4~6の整数である)、カーボネート基(-O-CO-O-)、エステル基(-CO-O-)、エーテル基(-O-)およびウレタン基(-NH-CO-O-)から成る群から選択される1以上の基を有していてもよく、かつ40~120の炭素原子を有する]を有するビニル化合物(dモル%)、
を含み、上記a~dが、a+b+c+d=100でありかつ下記式(1)~(3):
0<{b/(a+b)}x100≦5・・・(1)
3(c+d)/4≦(a+b)≦4(c+d) ・・・(2)
4d/3≦c≦40d ・・・(3)
を満たすところのフィルム。 - モノマー単位(D)におけるYが開環ラクトン基、カーボネート基、エステル基、エーテル基およびウレタン基から成る群から選択される1以上の基を有する、請求項1に記載のフィルム。
- 熱可塑性樹脂フィルムの少なくとも片面に請求項1または2に記載のフィルムを有する積層フィルム。
- 請求項1または2に記載のフィルムまたは請求項3に記載の積層フィルムからなる傷付き防止フィルム。
- 請求項4に記載の傷付き防止フィルムを有する物品。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/006,377 US9133289B2 (en) | 2011-03-22 | 2012-03-07 | Scratch-resistant film |
CN201280022823.3A CN103517933B (zh) | 2011-03-22 | 2012-03-07 | 膜及其制造方法、积层膜及其制造方法及物品 |
EP12760111.0A EP2690119B1 (en) | 2011-03-22 | 2012-03-07 | Scratch-resistant film |
KR1020137027387A KR101950531B1 (ko) | 2011-03-22 | 2012-03-07 | 스크래치 방지 필름 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011062883A JP5894741B2 (ja) | 2011-03-22 | 2011-03-22 | 傷付き防止フィルム |
JP2011-062883 | 2011-03-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012128050A1 true WO2012128050A1 (ja) | 2012-09-27 |
Family
ID=46879204
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/055871 WO2012128050A1 (ja) | 2011-03-22 | 2012-03-07 | 傷付き防止フィルム |
Country Status (7)
Country | Link |
---|---|
US (1) | US9133289B2 (ja) |
EP (1) | EP2690119B1 (ja) |
JP (1) | JP5894741B2 (ja) |
KR (1) | KR101950531B1 (ja) |
CN (1) | CN103517933B (ja) |
TW (1) | TWI526481B (ja) |
WO (1) | WO2012128050A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3900717A1 (en) | 2020-04-21 | 2021-10-27 | Immunic AG | Vidofludimus for use in the treatment or prevention of viral diseases |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5660970B2 (ja) * | 2011-05-13 | 2015-01-28 | リケンテクノス株式会社 | ハイグロスフィルムの施与方法 |
JP5321721B2 (ja) * | 2011-08-19 | 2013-10-23 | 富士ゼロックス株式会社 | 樹脂材料 |
EP3050701B1 (en) * | 2013-09-24 | 2019-07-03 | Toray Industries, Inc. | Laminated film |
KR102314335B1 (ko) * | 2014-01-31 | 2021-10-19 | 도레이 카부시키가이샤 | 적층 필름 |
CN116039378A (zh) * | 2014-05-15 | 2023-05-02 | Agc株式会社 | 玻璃物品以及玻璃物品的制造方法 |
KR102430212B1 (ko) * | 2015-03-30 | 2022-08-05 | 다이니폰 인사츠 가부시키가이샤 | 가식 시트 |
CN106671530A (zh) * | 2016-11-15 | 2017-05-17 | 合肥华凌股份有限公司 | 一种装饰膜及冰箱 |
US11299654B2 (en) | 2019-08-20 | 2022-04-12 | Roller Bearing Company Of America, Inc. | Permanent, self-adhering, self-lubricating, anti-wear composite system |
TW202311331A (zh) * | 2021-05-18 | 2023-03-16 | 日商Dic股份有限公司 | 含矽酮鏈的聚合物、塗敷組成物、抗蝕劑組成物及物品 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11228905A (ja) * | 1998-02-13 | 1999-08-24 | Natoko Kk | 塗料組成物 |
JP2001011376A (ja) * | 1999-07-02 | 2001-01-16 | Natoko Kk | 表面機能材料 |
JP2003118061A (ja) | 2001-10-15 | 2003-04-23 | Kansai Paint Co Ltd | 真珠光沢仕上げ調フィルム化粧材 |
JP2012053382A (ja) * | 2010-09-03 | 2012-03-15 | Konica Minolta Opto Inc | 太陽熱発電用光反射フィルム及び太陽熱発電用反射装置 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4728571A (en) * | 1985-07-19 | 1988-03-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer release coating sheets and adhesive tapes |
JPH0715015B2 (ja) * | 1989-06-30 | 1995-02-22 | 積水化学工業株式会社 | 熱硬化性被覆用シートと被覆物 |
JPH04292674A (ja) | 1991-03-19 | 1992-10-16 | Kansai Paint Co Ltd | 被覆用組成物 |
US5684084A (en) | 1995-12-21 | 1997-11-04 | E. I. Du Pont De Nemours And Company | Coating containing acrylosilane polymer to improve mar and acid etch resistance |
JPH11323263A (ja) * | 1998-05-19 | 1999-11-26 | Dainippon Printing Co Ltd | 転写用接着剤、それを用いた転写シートと転写方法 |
DE10048259A1 (de) * | 2000-09-29 | 2002-04-18 | Byk Chemie Gmbh | Beschichtungsmittel und polymere Formmassen mit anti-adhäsiven, schmutzabweisenden Eigenschaften |
JP2007063461A (ja) * | 2005-09-01 | 2007-03-15 | Daicel Chem Ind Ltd | 水酸基含有カプロラクトン変性(メタ)アクリレートモノマーとその製造方法、それを用いた反応性重合体、硬化性樹脂組成物およびその硬化物 |
JP5151209B2 (ja) * | 2007-03-29 | 2013-02-27 | Dic株式会社 | プライマー及び該プライマーからなる樹脂塗膜を有する積層体 |
-
2011
- 2011-03-22 JP JP2011062883A patent/JP5894741B2/ja active Active
-
2012
- 2012-03-07 US US14/006,377 patent/US9133289B2/en active Active
- 2012-03-07 EP EP12760111.0A patent/EP2690119B1/en not_active Not-in-force
- 2012-03-07 CN CN201280022823.3A patent/CN103517933B/zh not_active Expired - Fee Related
- 2012-03-07 KR KR1020137027387A patent/KR101950531B1/ko active IP Right Grant
- 2012-03-07 WO PCT/JP2012/055871 patent/WO2012128050A1/ja active Application Filing
- 2012-03-19 TW TW101109251A patent/TWI526481B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11228905A (ja) * | 1998-02-13 | 1999-08-24 | Natoko Kk | 塗料組成物 |
JP2001011376A (ja) * | 1999-07-02 | 2001-01-16 | Natoko Kk | 表面機能材料 |
JP3999411B2 (ja) | 1999-07-02 | 2007-10-31 | ナトコ株式会社 | 表面塗膜材料 |
JP2003118061A (ja) | 2001-10-15 | 2003-04-23 | Kansai Paint Co Ltd | 真珠光沢仕上げ調フィルム化粧材 |
JP2012053382A (ja) * | 2010-09-03 | 2012-03-15 | Konica Minolta Opto Inc | 太陽熱発電用光反射フィルム及び太陽熱発電用反射装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2690119A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3900717A1 (en) | 2020-04-21 | 2021-10-27 | Immunic AG | Vidofludimus for use in the treatment or prevention of viral diseases |
WO2021214033A1 (en) | 2020-04-21 | 2021-10-28 | Immunic Ag | Vidofludimus for use in the treatment or prevention of viral diseases |
Also Published As
Publication number | Publication date |
---|---|
EP2690119A4 (en) | 2014-09-17 |
CN103517933B (zh) | 2015-11-25 |
US20140057117A1 (en) | 2014-02-27 |
KR20140018300A (ko) | 2014-02-12 |
US9133289B2 (en) | 2015-09-15 |
TW201247750A (en) | 2012-12-01 |
TWI526481B (zh) | 2016-03-21 |
EP2690119A1 (en) | 2014-01-29 |
EP2690119B1 (en) | 2015-09-16 |
CN103517933A (zh) | 2014-01-15 |
JP2012197378A (ja) | 2012-10-18 |
KR101950531B1 (ko) | 2019-02-20 |
JP5894741B2 (ja) | 2016-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5894741B2 (ja) | 傷付き防止フィルム | |
JP6015877B1 (ja) | 加飾フィルムおよびその製造方法、並びに加飾成型体 | |
EP3279282A1 (en) | Coating agent, coating film, laminate, and surface-protected article | |
JP6543771B2 (ja) | 保護シート、物品および方法 | |
JP5167240B2 (ja) | 合成樹脂成形体及びこの成形体を成形するためのラミネートフィルムまたは転写フィルム | |
JP5951185B2 (ja) | 傷付き防止フィルム | |
JP2003313330A (ja) | ポリオレフィン系樹脂製積層フィルム | |
JP5882756B2 (ja) | 活性エネルギー線硬化性樹脂組成物 | |
JP2018065947A (ja) | アクリル系樹脂組成物、アクリル系フィルム、加飾フィルム及び加飾成型体 | |
JP7061531B2 (ja) | 硬化性樹脂組成物及び自己修復性材料 | |
TWI577733B (zh) | Active energy ray hardening resin composition | |
JP5937394B2 (ja) | 活性エネルギー線硬化性樹脂組成物 | |
JP2007197668A (ja) | マーキング用粘着シート | |
JP4354726B2 (ja) | ポリプロピレン樹脂マーキングフィルム | |
JP7109284B2 (ja) | 汚れ除去性塗膜形成用塗料、及びこれを用いた化粧シート | |
JP6880938B2 (ja) | 転写シート | |
JP2009202367A (ja) | 装飾用粘着シート | |
JP2008068627A (ja) | 可撓性をもつハードコートフィルム | |
JP4866573B2 (ja) | 高光沢化粧シート | |
WO2006004324A1 (en) | Reflector plate for lcd backlight and method of producing same | |
JP7157060B2 (ja) | 汚れ除去性塗膜形成用塗料、及びこれを用いた化粧シート | |
JP2002097422A (ja) | 粘着シート | |
JPWO2019131621A1 (ja) | 硬化性樹脂組成物及び自己修復性材料 | |
KR20230083114A (ko) | 코팅 조성물 및 이를 이용한 시트 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12760111 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012760111 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20137027387 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14006377 Country of ref document: US |