JP5255191B2 - Surface protective film for interior and exterior building materials and method for producing the same - Google Patents

Description

The present invention relates to a surface protective film for interior and exterior building materials and a method for producing the same.

Adhering a fluororesin film to the surface of a substrate such as plastic, metal, rubber, plywood, wood board, glass, printing paper, or slate to protect the substrate surface and provide weather resistance and contamination resistance, A method for imparting design properties to a substrate is known.

When a plastic plate or a metal plate is used as a base material, a method of thermally laminating a fluororesin film and the base material is widely used.

In order to enhance the luxury and design of the surface protective film, a film having a matte and low gloss surface is used. As a processing method for making the surface matt, for example, (1) when extruding a fluororesin film, passing an embossing roll immediately after extrusion to form irregularities on the surface (see Patent Document 1), (2) A method of adding an inorganic or organic substance to the fluororesin as a matting agent (3) A method of subjecting the film surface to physical treatment such as sandblasting or polishing after molding of the fluororesin film, (4) A film after molding of the fluororesin film For example, a method of coating a matting agent on the surface.

Among these processing methods, (1) the method of using an embossing roll and (2) the method of adding a matting agent may be used when the gloss returns to the surface when the fluororesin film and the substrate are heat laminated. In some cases, appearance defects (matte spots) may occur due to deterioration of dispersibility due to the addition of a matting agent, or mechanical strength may decrease.

A method of adding a cross-linked acrylic resin as a matting agent to a fluororesin film is known (see Patent Document 2, etc.).

Maintains the weather resistance and stain resistance, which are the characteristics of fluororesin films, is excellent in mass production, suppresses matting and mottling during thermal lamination, and is hard to decrease mechanical strength. There has been a demand for a surface protective film for interior / exterior building materials having the following.

Japanese Patent Laid-Open No. 02-28239 JP 2001-205755 A

Provided are a surface protective film for interior and exterior building materials and a method for producing the same.

This invention contains 1-10 mass parts of crosslinked acrylic resins with an average particle diameter of 1-10 micrometers with respect to a total of 100 mass parts of 90-85 mass parts of vinylidene fluoride resin and 10-15 mass parts of methacrylic ester resin. It is the surface protection film for interior / exterior building materials using a resin composition, and its manufacturing method.

The surface protective film for interior / exterior building materials of the present invention retains the weather resistance and stain resistance characteristic of a fluororesin film, has excellent mass productivity, has a matte-like low gloss surface, and is thermally laminated. It has features such as preventing gloss return and gloss spots, and reducing mechanical strength.

In the present specification, “part” and “%” are based on mass unless otherwise specified.

This invention contains 1-10 mass parts of crosslinked acrylic resins with an average particle diameter of 1-10 micrometers with respect to a total of 100 mass parts of 90-85 mass parts of vinylidene fluoride resin and 10-15 mass parts of methacrylic ester resin. It is the surface protection film for interior / exterior building materials using a resin composition, and its manufacturing method.

(Vinylidene fluoride resin)
The vinylidene fluoride resin is not particularly limited as long as it is a vinyl polymer having a vinylidene fluoride monomer unit, and may be a homopolymer of vinylidene fluoride. Vinylidene fluoride and other vinyl compound monomers The copolymer may be used. Examples of vinyl compound monomers that can be used in combination with vinylidene fluoride include fluorinated vinyl compounds such as vinyl fluoride, tetrafluoroethylene, ethylene trifluoride chloride, and hexafluoropropylene, styrene, ethylene, butadiene, And known vinyl monomers such as propylene.

(Methacrylic ester resin)
The methacrylate ester resin is not particularly limited as long as it is a vinyl polymer based on a methacrylate ester monomer. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate and the like, and methyl methacrylate is preferably used. The alkyl group such as propyl group, butyl group, pentyl group, and hexyl group of the methacrylic acid ester monomer may be linear or branched.

The methacrylate ester resin may be a monomer of a methacrylate ester monomer or a copolymer of a plurality of methacrylate ester monomers. The methacrylic ester resin may have a monomer unit derived from styrene, ethylene, butadiene, propylene and the like which are known vinyl compounds other than the methacrylic ester.

(Crosslinked acrylic resin)
The cross-linked acrylic resin is a copolymer of a methacrylic acid ester and a polyfunctional monomer.

Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

A polyfunctional monomer is a substance having two or more functional groups that can form a bond with another molecule by a chemical reaction other than a vinyl group, such as a hydroxyl group, a carboxyl group, an epoxy group, an amide group, A functional group-containing monomer having two or more functional groups selected from a functional group consisting of an amino group, a methylol group, a sulfonic acid group, a sulfamic acid group, and a (phosphite) ester group.

The polyfunctional monomer is not particularly limited, and examples thereof include ethylene glycol dimethacrylate, ethylene glycol bismethacrylate, propylene glycol diacrylate, trimethylolpropane trimethacrylate, and pentaerythritol tetramethacrylate.

The cross-linked acrylic resin may have a monomer unit derived from a known vinyl monomer such as ethylene or styrene. For the crosslinked acrylic resin, it is preferable to select a material that is dispersed without being compatible with the vinylidene fluoride resin and the methacrylic ester resin.

The cross-linked acrylic resin is a granular material having an average particle diameter (D ₅₀ ) of 1 to 10 μm in a laser scattering method (Mie scattering method) according to JIS Z8819 method, and preferably has an average particle diameter of 2 to 8 μm. If the average particle size is small, the glossiness of the surface may increase and the matte surface may not be obtained.If the average particle size is large, the dispersibility of the cross-linked acrylic resin will deteriorate, and a uniform matte surface cannot be obtained. Mechanical strength may decrease.

The composition of the resin constituting the surface protective film for interior / exterior building materials is an average particle diameter of 1 to 10 μm with respect to a total of 100 parts by mass of 90 to 85% by weight of vinylidene fluoride resin and 10 to 15% by weight of methacrylate ester resin. 1 to 10 parts by mass of the crosslinked acrylic resin. If the content of the vinylidene fluoride resin is large, it may be difficult to uniformly disperse the cross-linked acrylic compounded as a matting agent in the resin, and a good film surface appearance may not be obtained. When the content of vinylidene fluoride resin is small, the weather resistance and stain resistance of the surface protective film for interior and exterior building materials may be lowered.

The amount of the crosslinked acrylic resin used is 1 to 10 parts by mass, preferably 2 to 5 parts by mass, based on 100 parts by weight of the total amount of vinylidene fluoride resin and methacrylic ester resin. If the amount of the cross-linked acrylic resin used is small, a matte surface cannot be obtained, and if it is excessive, dispersibility is deteriorated and a uniform matte surface cannot be obtained, and the mechanical strength is lowered.

The particles of the cross-linked acrylic resin preferably have a shape with few surface irregularities, and are preferably, for example, spherical or elliptical rotating bodies. If the surface roughness of the cross-linked acrylic resin is large, the dispersibility of the vinylidene fluoride resin and methacrylic ester resin may decrease.

Although a ultraviolet absorber is not specifically limited, In order to have compatibility with resin to be used and to prevent volatilization of a ultraviolet absorber, a high molecular weight thing is preferable. As the ultraviolet absorber, for example, benzotriazole, oxalic acid, benzophenone, hindered amine, and the like can be used.

Examples of the benzotriazole-based ultraviolet absorber include 2- [3,5-di- (allopha-dimethylbenzyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxy]. Phenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 -[(2H-benzotriazol-2-yl) phenol]], 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol and the like.

Examples of the oxalic acid UV absorber include 2-ethoxy-2′-ethyl oxac acid bisanilide, 2-ethoxy-5-t-butyl-2′-ethyl oxac acid bisanilide, and the like. .

Examples of the benzophenone series include 2-hydroxy-4-n-octoxybenzophenone, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and bis (2,2,6,6-tetramethyl). -4-piperidinyl) sebacate, bis- (1-octyloxy-2,2,6,6, -tetramethyl-4-piperidinyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6- Tetramethyl-1-piperidinyl) ethanol, 1- [2-3- (3,5-di-t-butyl-4-hydroxyphenyl) poropionyloxy] -2,2,6,6-T-tetramethyl There are piperidine and the like.

Among these ultraviolet absorbers, use of a benzotriazole type is preferable because it shows remarkable weather resistance in a small amount. Although the usage-amount of a ultraviolet absorber is not specifically limited, If it is 0.01-5 mass parts of ultraviolet absorbers with respect to a total of 100 mass parts of vinylidene fluoride resin and methacrylic ester resin, it is a balance of a weather resistance and mechanical strength. Is preferable.

Surface protective films for interior and exterior building materials include antioxidants, dispersants, coupling agents, thermal stabilizers, surfactants, antistatic agents, antifogging agents, and colorants as complex oxide inorganic pigments and inorganic materials. Pigments, carbon black and pearl pigments may be used.

(Method for manufacturing surface protective film for interior and exterior building materials)
Although the manufacturing method of the surface protection film for interior / exterior building materials is not specifically limited, it can manufacture by melt extrusion molding, such as a T-die method, using a single screw extruder or a twin screw extruder.

The method of mixing vinylidene fluoride resin, methacrylic ester resin, cross-linked acrylic resin, and other additives is not particularly limited. For example, vinylidene fluoride resin or methacrylic ester resin that is a raw material in powder or pellet form A method in which a resin, a cross-linked acrylic resin and an additive are mixed in advance and melt-kneaded using a single screw extruder can be used.

Manufactures a compound made by pre-blending a part or all of vinylidene fluoride resin or methacrylate ester resin with crosslinked acrylic resin when adding vinylidene fluoride resin, methacrylate ester resin, or crosslinked acrylic resin Then, the compound and the remaining components may be melt kneaded with a single screw extruder.

The molding method of the surface protective film for interior / exterior building materials is not particularly limited, but it is preferable that one or both sides are matted with an embossing roll to form an embossed surface in order to make the surface have a good matte tone during extrusion molding. When one side is used as an embossed surface, it is pressure-bonded to an embossed roll and a metal roll so that the matte surface comes into contact with the embossed roll immediately after extrusion.

It is good to use what the following Formula (A) is materialized between the average particle diameter of the bridge | crosslinking acrylic resin of the surface protection film for interior / exterior building materials, and the surface roughness _{Rz of} an embossing roll.
Average particle diameter of cross-linked acrylic resin ≦ surface roughness R _{z of} embossing roll (Formula A)
When the film is heat laminated by hot roll pressing or hot press pressing, it is important that the average particle size of the crosslinked acrylic resin is equal to or less than the surface roughness of the embossing roll.

If the average particle diameter of the cross-linked acrylic resin is equal to or less than the surface roughness of the embossing roll, gloss return and luster are also suppressed by processing such as thermal lamination. The reason for this is that the convex portions of the surface irregularities formed by the embossing roll mainly contact with the surface of the hot roll or hot press preferentially. It is considered that the unevenness due to the cross-linked acrylic resin is present, so that the unevenness is maintained without being greatly influenced by the cushioning effect of the convex portion.

The D ₅₀ / R _z value, which is the ratio between the surface roughness R _z of the embossing roll and the average particle diameter D ₅₀ of the crosslinked acrylic resin, is not particularly limited, but the D ₅₀ / R _z value is preferably 1 or less. Is more preferably 0.8 or less, and most preferably 0.7 to 0.2. When the D ₅₀ / R _z value is large, the uneven portion due to the crosslinked acrylic resin itself is preferentially affected by the pinch pressure bonding rather than the surface unevenness due to the embossing roll at the time of heat lamination, which causes gloss return and gloss spots. There is a case. When the D ₅₀ / R _z value is small, the matting effect by the crosslinked acrylic resin itself is small, and a good matte surface cannot be obtained, and there is a possibility that it may cause matting at the time of heat processing.

The surface protective film for interior / exterior building materials of the present invention is preferable when a pattern is printed on the surface because it is excellent in design.

Although the film thickness of the surface protection film for interior / exterior building materials is determined according to various uses, it is 150 micrometers or less, Preferably, it is the range of 10-100 micrometers.

The surface protective film for interior / exterior building materials can be laminated on various substrates to form a laminate. Examples of the substrate include plastic, rubber, paint surface, metal, glass, wood, slate and the like. In order to laminate the base material and the surface protective film for interior / exterior building materials to form a laminate, there are a method of adhering the film to the base material using an adhesive and a method of heat-bonding.

As the adhesive used, general adhesives such as epoxy resin, acrylic resin, urethane resin, etc. can be used, and pressure sensitive adhesives using natural rubber, acrylic resin, etc. are used for interior and exterior building materials in advance. It can be used by being applied to the adhesive surface of the surface protective film. It is also possible to attach release paper to the pressure-sensitive adhesive, peel off the release paper at the time of use, and bond it to the substrate.

(Surface protection film for interior and exterior building materials)
For the purpose of improving durability and decoration, plastic plates, metal plates, and other various base materials used for interior and exterior parts of buildings have their surfaces painted, and surface protection films of durable films, especially fluororesins It is used by laminating. The use is wide, for example, for interior and exterior materials such as wallpaper, vehicles, and elevators, as well as for marking films, furniture, home appliances, trays and window glass.

(Examples 1 to 4, Comparative Examples 1 to 5) Each resin was blended with a tumbler at the blending ratios shown in Tables 1 and 2, and kneaded with a φ45 mm twin screw extruder to obtain a compound. Next, using a φ50 mm single screw extruder, a thin film having a film thickness ratio shown in Table 1 was formed. At this time, an embossing roll having a surface roughness shown in Table 1 was used. Next, for the films having good film appearance in Tables 1 and 2, the base materials shown in the tables were used, and after applying an acrylic resin adhesive on the film surface, heating lamination was performed. The heating laminate used a roll laminator and was thermally bonded under the condition of a heating temperature of 150 ° C. to obtain a laminated sheet.

(Materials used)
Vinylidene fluoride resins: Kyner K720 and Kyner K740, commercially available from Arkema.
Methacrylate ester resin: Hi-pet HBS000, manufactured by Mitsubishi Rayon Co., Ltd.
Cross-linked acrylic resin A: a copolymer of acrylic acid and ethylene glycol dimethacrylate, an average particle size (D ₅₀ ) of 8 μm, manufactured by Sekisui Plastics Co., Ltd., a commercial product.
Cross-linked acrylic resin B: copolymer of acrylic acid and ethylene glycol bismethacrylate, average particle size (D ₅₀ ) is 8 μm, manufactured by Soken Chemical Co., Ltd.
Cross-linked acrylic resin C: polymer of acrylic acid and pentaerythritol tetramethacrylate, average particle size (D ₅₀ ) is 1 μm, manufactured by Soken Chemical Co., Ltd.
Cross-linked acrylic resin D: polymer of acrylic acid and propylene glycol diacrylate, average particle size 9 μm, manufactured by Soken Chemical Co., Ltd.

(Evaluation)
The following items were evaluated for the thin film obtained in Examples and Comparative Examples and the heat-bonded laminated sheets. The results are shown in Tables 1 and 2.
1) Appearance The appearance of the obtained thin film was visually evaluated. The thin film films of Examples 1 to 4 and Comparative Examples 2 and 5 were films having a good low-gloss surface without poor dispersion of the matting agent. The thin film films of Comparative Examples 1, 3, and 4 deteriorated in appearance due to poor dispersion of the matting agent.

2) Surface glossiness The surface glossiness of the obtained thin film was measured using a gloss meter (Nippon Denshoku Co., Ltd. gloss meter VGS-1D). Examples 1 to 4 and Comparative Examples 2 and 5 were confirmed to have a low gloss surface. Since Comparative Example 1, 3 and 4 had a bad appearance, the evaluation was stopped.

3) Thermal processability The surface glossiness of the laminated sheet after heat lamination was measured using a gloss meter (Nippon Denshoku Co., Ltd. gloss meter VGS-1D). As a result of comparing the glossiness before heating lamination, it was confirmed that Examples 1 to 4 and Comparative Example 2 had little change in glossiness after heating lamination and excellent heat workability. As for Comparative Example 5, gloss return occurred and the glossiness increased.

4) Weather resistance The weather resistance of the obtained laminated sheet was measured according to JIS A1415 using a sunshine weatherometer. The appearance of the laminated sheet after 1000 hours was evaluated with a black panel temperature of 63 ° C. and a shower cycle of 18 minutes at intervals of 120 minutes. About Examples 1-4, it confirmed that the change on an external appearance was not seen after a test. In Comparative Example 2, the film was cracked.

In the present invention, the surface protective film for interior and exterior building materials retains the weather resistance and stain resistance characteristic of a fluororesin film, has an excellent mass productivity, has a matte-like low gloss surface, and is thermally laminated. It has features such as preventing glare and glare from being lost, and mechanical strength is unlikely to decrease, so it can be used for interior and exterior materials such as wallpaper, vehicle interior and exterior, elevator interior and exterior, as well as marking films, furniture, and home appliances. Suitable for applications such as trays and window glass.

Claims (7)

A resin composition containing 2 to 5 parts by mass of a crosslinked acrylic resin having an average particle diameter of 1 to 10 μm with respect to a total of 100 parts by mass of 90 to 85 parts by mass of a vinylidene fluoride resin and 10 to 15 parts by mass of a methacrylate ester resin. A surface protective film for interior and exterior building materials having a film thickness of 10 to 100 μm and using a single layer. The surface protective film for interior and exterior building materials according to claim 1, wherein the crosslinked acrylic resin is obtained by polymerizing a monomer containing a carboxyl group and a polyfunctional monomer. The surface protective film for interior and exterior building materials according to claim 1 or 2, wherein one or both surfaces are embossed surfaces. The interior / exterior building material according to any one of claims 1 to 3, wherein a D ₅₀ / R _Z value, which is a ratio of the surface roughness R _Z of the embossing roll and the average particle diameter D ₅₀ of the crosslinked acrylic resin, is 1 or less. Surface protective film. The surface protection film for interior / exterior building materials as described in any one of Claims 1 thru | or 4 formed by printing a design. The method for producing a surface protective film for interior / exterior building materials according to any one of claims 1 to 5, wherein one surface is pressure-bonded to an embossing roll during film formation. The laminated body formed by apply | coating an acrylic resin adhesive to the surface of the surface protection film for interior / exterior building materials as described in any one of Claims 1 thru | or 5, and heat-laminating with a base material.