JP5951185B2 - Scratch prevention film - Google Patents

Description

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. In particular, 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.

Conventionally, in order to provide functions such as scratch resistance, weather resistance, durability, contamination resistance, corrosion resistance, and designability to exterior parts such as automobile door sashes, 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.

In addition, 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.

However, such direct coating requires a number of processes such as masking, coating, curing, and finishing of the non-coated surface, and it is necessary to maintain a work environment and handle safety and health management to deal with paint solvents. In addition, there is a problem that skill is required to apply the coating uniformly without defects, and that the range of designability is limited in spray coating. In addition, the ultraviolet curable hard coat paint is liable to be deteriorated by ultraviolet rays, and satisfactory weather resistance cannot be obtained.

Therefore, it has been proposed to use a film decorative material instead of direct coating of paint (Patent Document 1). The use of 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.

In addition, as a surface coating material having improved scratch resistance, a composition containing a compound having a siloxane structure is widely used. This is because the above compound can improve the scratch resistance of the coating material by imparting lubricity to the surface of the coating material and lowering the coefficient of friction. However, a compound having a siloxane structure has a problem of bleeding out due to low compatibility and miscibility with other components and reducing stain resistance. A coating material obtained by curing a copolymer having a polydimethylsiloxane portion has also been proposed (Patent Document 2), but this coating material also has sufficient stain resistance due to the presence of a siloxane structure. It can not be said.

Japanese Patent Laid-Open No. 2003-118061 Japanese Patent No. 3999411

An object of the present invention is to provide a film that is useful as a means for replacing the direct coating of paints for surface protection and decoration of articles, and has excellent scratch resistance and stain resistance.

The inventor of the present invention, in a film comprising a crosslinked product of a composition comprising a vinyl compound copolymer and a polyisocyanate, comprises the above-mentioned copolymer comprising three specific types of monomer units, and thus has a siloxane structure such as polydimethylsiloxane. By not doing so, it was found that a film having excellent scratch resistance, particularly scratch recovery properties, and excellent stain resistance was obtained, and the present invention was achieved.

Scratch resilience means that when external pressure is applied to the film surface, it immediately elastically deforms and does not easily break, and after the external pressure is removed, the deformation is restored without remaining as plastic deformation. It means the nature.

That is, the present invention provides a film comprising a crosslinked product of a composition comprising a vinyl compound copolymer and a polyisocyanate, wherein the vinyl compound copolymer comprises the following monomer units:
(A) a vinyl compound having no hydroxyl group (a mol%),
(B) a vinyl compound (b mol%) having a linear or branched alkyl group having a hydroxyl group, the alkyl group having 1 to 6 carbon atoms, and (C) the following formula:
_{CH 2 = C (R) -COO} -Y
[Wherein R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y is optionally a ring-opening lactone group (—CO— (CH ₂ ) n -O-, where n is an integer from 4 to 6, carbonate groups (-O-CO-O-), ester groups (-CO-O-), ether groups (-O-) and urethane groups ( A vinyl compound (c mol%) which may have one or more groups selected from the group consisting of —NH—CO—O—) and has 25 to 120 carbon atoms]
Wherein a to c are a + b + c = 100 and the following formulas (1) and (2):
3 (b + c) / 4 ≦ a ≦ 4 (b + c) (1)
4c / 3 ≦ b ≦ 40c (2)
And the film has a thickness of 10 to 30 μm, is scratch resistant and has an embossed pattern on one surface.
The present invention also provides a laminated film having the above-mentioned film on at least one surface of the thermoplastic resin film so that the surface not having an embossed pattern is in contact with the thermoplastic resin film.

Since the film and laminated film of the present invention exhibit viscoelastic behavior of a forked model, it has excellent scratch recovery and stain resistance, as well as excellent weather resistance, chemical resistance, bending resistance and impact resistance. For example, it is useful as an anti-scratch film or a decorative film as an alternative to direct coating of paint on the surface of an article, for example, on 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 copolymer comprises the following monomer units (A) to (C).

Monomer (A)
The monomer (A) is a vinyl compound having 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, and tetrahydro. (Meth) acrylic acid 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 α-methylstyrene; cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile; vinyl acetate and the like Rubonic acid vinyl ester; Halogen-containing vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; Epoxy group-containing vinyl compounds such as glycidyl (meth) acrylate and allyl glycidyl ether; Acrylic acid and methacrylic acid, etc. 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.

Monomer (B)
The monomer (B) 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 ( B ) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate. , Hydroxyethyl acrylamide, and allyl alcohol, among which acrylic acid 2-hydroxyethyl ester and methacrylic acid 2-hydroxyethyl ester are preferable.

Monomer (C)
The monomer (C) has the following formula:
_{CH 2 = C (R) -COO} -Y
It is a vinyl compound. R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, Y is optionally a ring-opening lactone group (—CO— (CH ₂ ) n—O—, Here, n is an integer of 4 to 6), carbonate group (—O—CO—O—), ester group (—CO—O—), ether group (—O—) and urethane group (—NH—CO). -O-) (hereinafter may be referred to as "ring-opening lactone group and the like") may have one or more groups selected from the group consisting of 12 to 120 carbon atoms. If the carbon number of Y is too small, the resulting film has poor scratch recovery properties, and if too large, the stain resistance is poor. Carbon number of the said alkyl group becomes like this. Preferably it is 25-90, More preferably, it is 36-90, More preferably, it is 40-90.

Monomer (C) is, for example, (meth) acrylic acid and a long-chain glycol having hydroxyl groups at both ends represented by the formula OH-Y, such as a long-chain glycol having a molecular weight of 202 to 1714 (carbon number 12 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 (C) 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 performed 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. . Examples of the polycaprolactone diol include Plaxel 205 (carbon number 26), Plaxel 210 (carbon number 50), and Plaxel 220 (carbon number 104) manufactured by Daicel Chemical Industries, Ltd. Moreover, as a commercial example of the monomer (C) in which Y has a poly ring-opening lactone structure, for example, Plaxel FM5 (caprolactone 5 mol addition product of hydroxyethyl methacrylate, manufactured by Daicel Chemical Industries, Ltd., CH ₂ ═C (CH ₃ ) — COO—C ₂ H ₄ —O— (CO—C ₅ H ₁₀ —O) ₅ —H, Y carbon number 32) and Plaxel FA10L (hydroxypropyl acrylate 10 mol caprolactone adduct, CH ₂ ═CH—COO—C ₂ H ₄ —O— (CO—C ₅ H ₁₀ —O) ₁₀ —H, Y has 62 carbon atoms).

Moreover, the monomer (C) in which Y has a polycarbonate structure can be manufactured by dehydration condensation of (meth) acrylic acid and polycarbonate diol. Examples of the polycarbonate diol include Plaxel CD205 (carbon number 27), Plaxel CD210 (carbon number 48) and Plaxel CD220 (carbon number 97) manufactured by Daicel Chemical Industries, Ltd.

Manufactured by NOF CORPORATION of Blemmer _{PP-800 (CH 2 = CH} -COO- (C 3 H 6 -O) 13 -H, polypropylene glycol monoacrylate) can also be used as monomer (C).

The vinyl compound copolymer in the present invention is obtained by copolymerization of the monomers (A) to (C). When the amounts of the monomers (A) to (C) are a mol%, b mol% and c mol%, respectively, it is necessary that a + b + c = 100 and satisfy the following formulas (1) and (2). is there.
3 (b + c) / 4 ≦ a ≦ 4 (b + c) (1)
4c / 3 ≦ b ≦ 40c (2)

Formula (1) shows the relationship between the molar amount (a) of the monomer (A) having no hydroxyl group and the total molar amount (b + c) of the monomers (B) and (C) having a hydroxyl group. Since a + b + c = 100, using the relational expression b + c = 100−a, the expression (1) means 42.9 ≦ a ≦ 80. Therefore, 20 ≦ b + c ≦ 57.1.

Regarding a formula (1), when a> 4 (b + c) (that is, when a> 80), the crosslink density is too low and the stain resistance, heat resistance, weather resistance and chemical resistance are lowered. When 3 (b + c) / 4> a (that is, when a <42.9), the crosslink density is too high, and a rigid and glass-like cured film is provided, so that the scratch recovery property does not appear. Preferably, Formula (1) is 5 (b + c) / 6 ≦ a ≦ 5 (b + c) / 2. This means that 45.5 ≦ a ≦ 71.4 using the relational expression b + c = 100−a. Therefore, 28.6 ≦ b + c ≦ 54.5.

Formula (2) shows the relationship between the molar amounts of the monomers (B) and (C) having a hydroxyl group. Regarding formula (2), when 4c / 3> b, that is, when the amount of the monomer (B) is too small or the amount of the monomer (C) is too large, the crosslinking density becomes too low, and stain resistance and heat resistance are reduced. , Weather resistance and chemical resistance are reduced. When b> 40c, that is, when the amount of the monomer (B) is too large or the amount of the monomer (C) is too small, the crosslink density becomes too high, giving a rigid and glass-like cured film, so that the scratch recovery property is obtained. No longer develops. In addition, bending resistance and impact resistance may be reduced. Preferably, b and c satisfy 8c / 5 ≦ b ≦ 8c, more preferably 2c ≦ b ≦ 4c.

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. If necessary, 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. Moreover, the film of this invention is obtained by peeling a thermoplastic resin film from the said laminated | multilayer film.

There is no restriction | limiting in particular in the coating method, 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 coating film is preferably 10 to 100 μm 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, and specifically includes methylene bis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of tolylene diisocyanate, and 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. Preferably, 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. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate and dibutyltin diethylhexoate may be added as necessary.

The amount of polyisocyanate is preferably a 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, preferably 1: 0.7 to 1: 1.4, more preferably 1: 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. For example, room temperature drying can be performed over 6 hours to 1 week. Heat drying can be performed at 40 to 300 ° C. for 5 seconds to 120 minutes. Desirably, 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. Furthermore, when heat drying is performed on a thermoplastic resin film having a low softening point, the thermoplastic resin film is softened during the drying process, which may cause problems such as blurring, wrinkling, and shrinkage. In order to prevent this, 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.

Examples of the thermoplastic resin film to which the paint is applied 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), styrene resins such as styrene / ethylene / butadiene / styrene copolymers and hydrogenated products thereof, and films of 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. In addition, when 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 μm, and preferably 75 in consideration of application to vacuum molding, membrane press molding, pressure press molding, in-mold molding, insert molding, and the like described later. ˜300 μm.

Moreover, when embossing is performed on the surface opposite to the thermoplastic resin film of the laminated film of the present invention (ie, the coating film surface) for the purpose of imparting design properties, the coating film is elastically deformed. However, embossing may be difficult, but the thickness of the coating film is 10 to 30 μm, the thickness of the thermoplastic resin film is 80 to 300 μm, and the surface roughness Rz is 20 μm 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. For example, it is useful as an anti-scratch film or a decorative film. For example, 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.

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. When 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. On the other hand, when such air gap grooves are provided, there is a possibility that an appearance defect that a recess corresponding to the groove on the film surface of the present invention is formed, and in order to prevent it, the design of the air groove is The width of the groove is preferably 10 to 200 μm, more preferably 50 to 150 μm. Further, the depth of the groove is preferably 5 to 50 μm, more preferably 10 to 30 μm, and the cross-sectional shape thereof is semicircular. Furthermore, in order to efficiently discharge bubbles without causing appearance defects, the pressure-sensitive adhesive layer separated by the grooves when the surface of the pressure-sensitive adhesive layer having 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.

In addition, when the film or laminated film of the present invention is 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. In the case of performing integral molding, it is preferable that 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. When vacuum forming is performed, it is necessary to follow the complicated shape of the member. Therefore, the glass transition point of the thermoplastic resin film is preferably 60 to 130 ° C., specifically acrylic resin, polyvinyl chloride. Resin, polyester resin and acrylonitrile / butadiene / styrene copolymer resin films are preferred. In addition, since the laminated film is stretched in vacuum forming, in the film of the present invention, 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Production 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 mol% monomers (A), (B) and (C-1) shown in Table 1 (that is, 29 parts by mass of monomer (A), 15 parts by mass of monomer (B) and monomer (C -1) 57 parts by mass) and 1 part by mass of 2,2′-azobisisobutyronitrile (manufactured by Nippon Finechem Co., Ltd., ABN-R), this mixture was mixed in 100 ° C. methyl isobutyl ketone for 3 hours. It was dripped over. The mixture was further refluxed for 6 hours to obtain the desired copolymer (solid content 50%).

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 μm 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.

Production Examples 2, 3 and 5-13 and Comparative Production Examples 1-7
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 Production 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 μm. 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. The following tests (1) to (13) were performed on the obtained laminated film. The results are shown in Table 1.

The materials used are as follows.
Monomer (A): Mitsubishi Rayon Co., Ltd., methyl methacrylate monomer (B): Nippon Shokubai Co., Ltd., 2-hydroxyethyl methacrylate, carbon number 2 of hydroxyl group-containing alkyl group
Monomer (C-1): Plaxel FA10L manufactured by Daicel Chemical Industries, Ltd., adduct of 10 mol of caprolactone of hydroxyethyl acrylate, 62 carbon atoms of Y, molecular weight 1256
Monomer (C-2): Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd., 5 mol adduct of caprolactone of hydroxyethyl methacrylate, 32 carbon atoms of Y, molecular weight of 700
Monomer (C-3): Plaxel FM3 manufactured by Daicel Chemical Industries, Ltd., 3 mol adduct of caprolactone of hydroxyethyl methacrylate, Y 20 carbon atoms, molecular weight 472
Monomer (C-4): Dehydrated condensate of Plaxel CD210 (polycarbonate diol, HO— (C ₆ H ₁₂ —O—CO—O) ₆ —C ₆ H ₁₂ —OH) and acrylic acid manufactured by Daicel Chemical Industries, Ltd. , Y carbon number 48, molecular weight 1036
Monomer (C-5): Dehydrated condensate of Plaxel CD220 (polycarbonate diol, HO— (C ₆ H ₁₂ —O—CO—O) ₁₃ —C ₆ H ₁₂ —OH) and acrylic acid manufactured by Daicel Chemical Industries, Ltd. , Y carbon number 97, molecular weight 2044
Monomer (C-6): Compound prepared by the following method, Y 46 carbon atoms, molecular weight 1002
Comparative monomer (C): Placel 230 (polycaprolactone diol, carbon number 158) manufactured by Daicel Chemical Industries, Ltd. and a dehydration condensate of acrylic acid, carbon number 158 of Y, molecular weight 3096
Siloxane compound: X-22-22426 manufactured by Shin-Etsu Chemical Co., Ltd., one-end methacryl-modified polydimethylsiloxane, molecular weight: about 14000
Polyisocyanate: Coronate HX manufactured by Nippon Polyurethane Industry, solid content 100%, NCO content 21.3% by mass

Preparation of monomer (C-6) Plaxel FM2D (caprolactone 2 mol adduct of hydroxyethyl methacrylate, molecular weight 358) manufactured by Daicel Chemical Industries, Ltd. and adipic acid (molecular weight 146) were dehydrated using an acid catalyst. To synthesize terminal carboxylic acid-modified methacrylate. Subsequently, Placel 205 (diol of caprolactone tetramer, H— {O (CH ₂ ) ₅ CO} ₂ —O—CH ₂ —O—CH ₂ —, manufactured by Daicel Chemical Industries, Ltd., was added to the terminal carboxylic acid-modified methacrylate. O— {CO (CH ₂ ) ₅ O} ₂ —H, molecular weight 534) was added, and dehydration condensation was performed using an acid catalyst to obtain a terminal hydroxyl group-containing methacrylate monomer (C-6).

Test (1) Abrasion Restoration Property 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. In the case of the laminated film (b), it was placed so that the coating surface was the surface. Using 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.
Δ: Scratch disappeared within 1 minute to 24 hours.
X: The scratch did not disappear even after 24 hours.

(2) Scratch resistance against friction The film (b) or the laminated film (b) obtained above was cut into a length of 200 mm and a width of 25 mm to obtain a test piece, which was placed in a JIS L 0849 Gakushin Tester. . In the case of the laminated film (b), it was placed so that the coating surface was the surface. Subsequently, after attaching the gold width No. 3 to the friction terminal of the Gakushin Tester in a 5-fold manner, the surface of the test piece after 100 reciprocations with a 500 gf load was confirmed.
A: No scratch was observed.
○: Less than 10 minor scratches were observed on the coating film surface.
Δ: 10 or more minor scratches were observed on the coating film surface.
X: A clear scratch was observed on the entire coating film surface.

(3) Bending resistance The film (I) or the laminated film (B) obtained above was cut into a size of 100 mm × 50 mm, and a double-sided tape No. 2 manufactured by Nitto Denko Corporation was used. A test piece was affixed to an aluminum plate having a thickness of 0.3 mm using 500A. In the case of a laminated film (b), it was pasted so that the coating film surface was the surface. Using a JIS K 5600-5-1 type 1 bending test apparatus to which a mandrel having a diameter of 2 mm is attached, the test piece is turned to 180 ° at an even speed over 2 seconds so that the coating surface is on the outside. Bent. After completion of the bending, the presence or absence of cracks in the coating film was confirmed for the central 30 mm portion of the bent portion.
○: No cracking occurred.
(Triangle | delta): Although a crack does not arise, the bent part became whitish.
X: Cracking occurred.

(4) Impact resistance The film (I) or laminated film (B) obtained above was cut into a size of 100 mm x 50 mm, and double-sided tape No. 2 manufactured by Nitto Denko Corporation was used. Using 500A, it affixed on the 150 mm x 75 mm x 1 mm aluminum plate, and was set as the test piece. In the case of a laminated film (b), it was pasted so that the coating film surface was the surface. This test piece is placed on a DuPont impact tester with a φ1 / 4 inch steel ball attached according to JIS K 5600-5-3 so that the coating surface faces upward, and a weight with a load of 300 gf is 20 cm high. Then, after dropping and giving an impact, the presence or absence of cracks in the coating film was evaluated.
○: No cracking occurred.
X: Cracking occurred.

(5) Water resistance Using the test piece similar to the above test (4), this was taken out after being immersed in warm water at 40 ° C. for 168 hours, and the appearance of the coating film was visually evaluated within 1 hour according to the following criteria. .
○: No change was observed.
(Triangle | delta): Although it cannot confirm with the naked eye, there exist very small swelling, peeling, or a crack of the grade which can be confirmed using a microscope, The slight gloss fall and stain resulting from these were confirmed with the naked eye.
X: Swelling, peeling or cracking was confirmed with the naked eye.

(6) Moisture resistance Using the same test piece as in the above test (4), this was left in a constant temperature and humidity chamber at 50 ° C. and 95% RH for 168 hours and then taken out. Visual evaluation was performed according to the same evaluation criteria as in (5).

(7) Heat resistance Using the same test piece as in the above test (4), this was left in a gear oven at 100 ° C. for 1 hour, then taken out, and further left at room temperature for 1 hour or more. Visual evaluation was performed according to the same evaluation criteria as in (5).

(8) Acid resistance Using the same test piece as in the above test (4), 2 ml of 10% dilute sulfuric acid was added dropwise and allowed to stand at room temperature for 24 hours, followed by thorough washing with water. The test piece was further allowed to stand at room temperature for 1 hour or longer, and then the appearance of the coating film was visually evaluated according to the same evaluation criteria as in Test (5).

(9) Base resistance Using the same test piece as in the above test (4), 2 ml of 5% aqueous sodium carbonate solution was added dropwise thereto and allowed to stand at 40 ° C. for 6 hours, and then thoroughly washed with water. The test piece was further allowed to stand at room temperature for 1 hour or longer, and then the appearance of the coating film was visually evaluated according to the same evaluation criteria as in Test (5).

(10) Gasoline resistance Using the same test piece as in the above test (4), 2 ml of No. 1 gasoline according to JIS K 2202 was added dropwise and allowed to stand at room temperature for 24 hours, and then thoroughly washed with water. The test piece was further allowed to stand at room temperature for 2 hours or more, and then the appearance of the coating film was visually evaluated according to the same evaluation criteria as in Test (5).

(11) Alcohol resistance Using the same test piece as in the above test (4), 2 ml of ethanol was added dropwise thereto and allowed to stand at room temperature for 24 hours, and then thoroughly washed with water. The test piece was further allowed to stand at room temperature for 24 hours or more, and then the appearance of the coating film was visually evaluated according to the same evaluation criteria as in Test (5).

(12) Weather resistance Using the same test piece as in the above test (4), this was exposed with a sunshine weatherometer for 2000 hours, and then thoroughly washed with water. The test piece was further allowed to stand at room temperature for 24 hours or more, and then the appearance of the coating film was visually evaluated according to the same evaluation criteria as in Test (5).

(13) Contamination resistance Two test pieces similar to those in the above test (4) were prepared, and these were left outdoors for 180 days and 360 days, respectively, and then sufficiently washed with water. After these test pieces were further allowed to stand at room temperature for 24 hours or more, the appearance of the coating film was visually evaluated according to the following evaluation criteria.
○: No change in appearance was observed in either test piece.
(Triangle | delta): Gloss fall, swelling, or peeling was confirmed only to the test piece left to stand for 360 days.
X: In both test pieces, gloss reduction, swelling or peeling was confirmed.

(14) The handling film (b) or the laminated film (b) is cut out to 100 × 25 mm, and this is attached to an A & D Tensilon RTG-1310 tensile tester with a distance between chucks of 50 mm, and pulled at a pulling speed of 200 mm / min. The 10% modulus value when the 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 10 N / 25 mm or more
Δ: 10% modulus value is 1 N / 25 mm or more and less than 10 N / 25 mm
X: 10% modulus value is less than 1 N / 25 mm

As shown in Table 1, the film and laminated film of the present invention are excellent in scratch recovery properties and stain resistance, and are also excellent in weather resistance, chemical resistance, bending resistance and impact resistance.

On the other hand, in Comparative Production Example 1 in which a does not satisfy the formula (1) and the amount of the monomer (A) is too large, the chemical resistance, weather resistance and stain resistance are inferior, and the amount of the monomer (A) is too small. In Production Example 2, the scratch resilience was poor. In Comparative Production Example 3 where b and c do not satisfy formula (2) and the amount of monomer (B) is too large, the amount of monomer (B) is too small because of poor scratch recovery, bending resistance and impact resistance. In Comparative Production Example 4, the stain resistance was poor. In Comparative Production Example 5 using the monomer (C) having a terminal hydroxyl group-containing alkyl group having more carbon atoms than the range of the present invention, the stain resistance was poor. In Comparative Production Example 6 in which the vinyl compound copolymer had a siloxane structure, the stain resistance was poor.

Example 14
100 parts by mass of vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., degree of polymerization 1100), 20 parts by mass of 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 μm). A film obtained in the same manner as in Production Example 1 except that the thickness of the coating film was 15 μm 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 μm at 100 ° C. and 5 kgf / cm ² on the surface of the coating film.

Example 15
Embossed film 2 was obtained in the same manner as in Example 14 except that the coating film thickness was 25 μm in Example 14.

Example 16
Embossed film 3 was obtained in the same manner as in Example 14 except that the thickness of the base film was changed to 250 μm in Example 14.

Example 17
In Example 14, 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 14 except that the product was manufactured using an extrusion die molding machine (thickness: 100 μm).

Reference example 1
Embossed film 5 was obtained in the same manner as in Example 14 except that the surface roughness Rz of the embossing roll was 10 μm in Example 14.

Reference example 2
Embossed film 6 was obtained in the same manner as in Example 14 except that the coating film thickness was changed to 5 μm in Example 14.

Reference example 3
Embossed film 7 was obtained in the same manner as in Example 14 except that the coating film thickness was 40 μm in Example 14.

Comparative Example 7
Example 14 with the exception of using 100 parts by weight of ALLEX26 K-37 (trade name) manufactured by Nippon Kaiko Paint Co., Ltd. and 10 parts by weight of ALLEX26 curing agent, which does not have scratch resilience, as a paint for the coating film. In the same manner, an embossed film 8 was obtained.

The embossed films 1 to 8 obtained above were subjected to the following embossability test and the above tests (1) and (13). 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.

Claims (7)

In a film comprising a crosslinked product of a composition comprising a vinyl compound copolymer and a polyisocyanate, the vinyl compound copolymer comprises the following monomer units:
(A) a vinyl compound having no hydroxyl group (a mol%),
(B) a vinyl compound (b mol%) having a linear or branched alkyl group having a hydroxyl group, the alkyl group having 1 to 6 carbon atoms, and (C) the following formula:
_{CH 2 = C (R) -COO} -Y
[Wherein R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y is optionally a ring-opening lactone group (—CO— (CH ₂ ) n -O-, where n is an integer from 4 to 6, carbonate groups (-O-CO-O-), ester groups (-CO-O-), ether groups (-O-) and urethane groups ( A vinyl compound (c mol%) which may have one or more groups selected from the group consisting of —NH—CO—O—) and has 25 to 120 carbon atoms]
Wherein a to c are a + b + c = 100 and the following formulas (1) and (2):
3 (b + c) / 4 ≦ a ≦ 4 (b + c) (1)
4c / 3 ≦ b ≦ 40c (2)
And the film has a thickness of 10 to 30 μm, is scratch resistant and has an embossed pattern on one surface. The film according to claim 1, wherein Y in the monomer unit (C) has one or more groups selected from the group consisting of a ring-opening lactone group, a carbonate group, an ester group, an ether group and a urethane group. A laminated film having the film according to claim 1 or 2 on at least one surface of a thermoplastic resin film so that a surface not having an embossed pattern is in contact with the thermoplastic resin film. A method for producing a film comprising a crosslinked product of a composition comprising a vinyl compound copolymer and a polyisocyanate, wherein the vinyl compound copolymer comprises the following monomer units:
(A) a vinyl compound having no hydroxyl group (a mol%),
(B) a vinyl compound (b mol%) having a linear or branched alkyl group having a hydroxyl group, the alkyl group having 1 to 6 carbon atoms, and (C) the following formula:
_{CH 2 = C (R) -COO} -Y
[Wherein R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y is optionally a ring-opening lactone group (—CO— (CH ₂ ) n -O-, where n is an integer from 4 to 6, carbonate groups (-O-CO-O-), ester groups (-CO-O-), ether groups (-O-) and urethane groups ( A vinyl compound (c mol%) which may have one or more groups selected from the group consisting of —NH—CO—O—) and has 25 to 120 carbon atoms]
Wherein a to c are a + b + c = 100 and the following formulas (1) and (2):
3 (b + c) / 4 ≦ a ≦ 4 (b + c) (1)
4c / 3 ≦ b ≦ 40c (2)
In the manufacturing method in which the film has a thickness of 10 to 30 μm, is scratch resistant , and has an embossed pattern on one surface, an embossing roll having a surface roughness Rz of 20 μm or more is used. Forming an embossed pattern. At least one surface of the thermoplastic resin film has a thickness of 10 to 30 μm , is scratch-resistant, and has a film having an embossed pattern on one surface, and the surface not having the embossed pattern is in contact with the thermoplastic resin film. A method for producing a laminated film as described above, wherein the film having an embossed pattern comprises a cross-linked product of a composition comprising a vinyl compound copolymer and a polyisocyanate, and the vinyl compound copolymer comprises the following monomer units:
(A) a vinyl compound having no hydroxyl group (a mol%),
(B) a vinyl compound (b mol%) having a linear or branched alkyl group having a hydroxyl group, the alkyl group having 1 to 6 carbon atoms, and (C) the following formula:
_{CH 2 = C (R) -COO} -Y
[Wherein R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y is optionally a ring-opening lactone group (—CO— (CH ₂ ) n -O-, where n is an integer from 4 to 6, carbonate groups (-O-CO-O-), ester groups (-CO-O-), ether groups (-O-) and urethane groups ( A vinyl compound (c mol%) which may have one or more groups selected from the group consisting of —NH—CO—O—) and has 25 to 120 carbon atoms]
Wherein a to c are a + b + c = 100 and the following formulas (1) and (2):
3 (b + c) / 4 ≦ a ≦ 4 (b + c) (1)
4c / 3 ≦ b ≦ 40c (2)
In the manufacturing method which satisfy | fills, forming the embossing pattern using the embossing roll which has the surface roughness Rz of 20 micrometers or more, The said method.
Article having the film of claim 1 or 2. An article comprising the laminated film according to claim 3 .