JPH0452287B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a super weather-resistant film made by coating a vinyl chloride resin film with ultraviolet blocking performance with a special fluorine-based resin soluble in a solvent. The super weather-resistant film of the present invention exhibits particularly excellent performance as a coating film for steel plates, aluminum plates, resin-coated metal plates, resin products, and the like. Conventionally, fluororesin films such as vinyl fluoride resin and vinylidene fluoride resin have been known as the films with the best weather resistance, but these films are expensive and the films themselves have excellent weather resistance. However, the effectiveness of protecting the coated object was poor. That is, for example, when a transparent film of vinylidene fluoride resin is laminated on a PVC-coated steel plate, the surface of the vinylidene fluoride resin film exhibits long-term weather resistance, but the weather resistance of the PVC-coated steel plate itself does not improve. It has the disadvantage that it discolors significantly after several years of aging. Also, when a fluororesin film is bonded directly to a steel plate with an epoxy adhesive,
Although the film itself does not change over time, deterioration of the adhesive causes the film to peel off, resulting in a practically serious defect. The object of the present invention is that the film itself has the same weather resistance as the above-mentioned fluororesin film, and
The object of the present invention is to provide a super weather-resistant film that can protect a covering to a much greater degree than the fluororesin film. Another object of the present invention is to provide an excellent ultra-weather-resistant film that is less expensive than the fluororesin film described above and exhibits excellent lamination and adhesive properties. . That is, the present invention is a super weather-resistant film made by coating a solvent-type fluorine-based resin on a vinyl chloride-based resin film containing an ultraviolet absorber. Other advantages of the super weather resistant film of the present invention will become clearer from the description below. The “solvent-type fluororesin” used in the present invention is
Tetrafluoroethylene (TEE), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF),
Monomers copolymerizable with one or more fluoroolefins such as vinylidene fluoride (VdF); for example, olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinyl halides such as vinylidene chloride , ethyl acrylate,
Methyl methacrylate, reactive methacrylate,
One type of unsaturated carboxylic acid esters such as polyfunctional acrylates, vinyl carboxylates such as vinyl acetate and vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, fluorovinyl ether, etc. Or a copolymer resin with two or more types of monomers, such as ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), esters such as methyl acetate, ethyl acetate, butyl acetate, toluene, xylene, etc. This refers to resins that are soluble in general organic solvents such as aromatic compounds, mineral spirits, butyl alcohol, etc. Generally, the resin composition is as follows:
It is preferable that the amount of the fluorine-based monomer is about 25 to 80% by weight. The molecular weight of the above solvent type fluororesin is 10,000.
-80000, fluorine content 20-45% by weight, and hydroxyl value (OHV) (value expressed in mg of caustic potassium having the same number of moles as hydroxyl groups contained in 1 g of resin) are preferably 30-70. . Furthermore, it may contain other polar groups. When crosslinking this, examples of crosslinking agents include methylated melamine (e.g. CYMEL 325), butylated melamine (e.g. UBAN 20 SE 60), isocyanate (e.g. DESMODURN), etc., which react and cure at low temperatures, and can be used relatively easily. This is good because it provides a coating film that firmly adheres to the vinyl chloride resin film used in the invention and exhibits excellent super weather resistance. As the solvent-type fluororesin used in the present invention, from the viewpoint of the softening point of the vinyl chloride resin film, etc.
A low-temperature crosslinking product that is prepared by mixing an appropriate amount of crosslinking agent with a solvent-type fluororesin and curing at preferably 0°C to 150°C, more preferably 5°C to 100°C, particularly preferably 5°C to 80°C. Solvent-type fluororesins are preferred. As these low-temperature crosslinkable solvent-based fluorocarbon resins, for example, the solid content concentration of solvent-based fluorocarbon resins is 40%.
~60% by weight, solvent MIBK/xylene = 50/50, solution viscosity approximately 100C.PS, butylated melamine 20 parts by weight per 100 parts by weight of solvent-type fluororesin, and others that can be added. . Depending on the purpose of use of the ultra-weather-resistant film, if desired, commonly used additives other than those mentioned above, such as colorants (dyes, pigments, etc.),
Although ultraviolet absorbers and other resins can be blended, the thickness of the coating film formed after applying the solvent-based fluororesin is determined by the excellent weather resistance of the vinyl chloride resin film used in the present invention. From a viewpoint, 2 to 30μ is generally sufficient, and including economical viewpoint, 5μ is sufficient.
-20μ is preferred, and 5-15μ is particularly preferred.
If the thickness of the coating film is less than 2μ, no protective effect can be expected, and if it exceeds 30μ, it is too thick and economically useless. The "ultraviolet absorber" used in the present invention is not particularly limited as long as it is compatible with vinyl chloride resin, and it can be used alone or in combination of two or more, but these As an example, 2-
(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-
di-tert-butyl-phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-
Methyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy Benzotriazole UV absorbers such as -4'-n-octoxy phenyl) benzotriazole; 2,4-dihydroxy benzophenone, 2-hydroxy-4-
Methoxy benzophenone, 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfonate benzophenone, 2-hydroxy-
4-methoxy-2'-carboxy benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxy benzophenone, 2-
Hydroxy-4-octadecyloxy benzophenone, 2,2',4,4'-tetrahydroxy benzophenone, 4-dodecyloxy-2-hydroxy benzophenone, 2-hydroxy-4-(2
Benzophenone UV absorbers such as -hydroxy-3-methacryloxy)propoxybenzophenone; Salicylic acid derivative UV absorbers such as phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate; oxalic acid anilide Derivatives, resorcinol
Monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-ethyl-hexyl-2-cyano-3,3 diphenyl acrylate, ethyl-2- Other UV absorbers may be mentioned, such as cyano-3,3-diphenyl acrylate. Among these UV absorbers, 2'-hydroxyphenyl-5-chlorobenzotriazole UV absorbers, 2'-hydroxyphenylbenzotriazole UV absorbers, and 2,2'-dihydroxybenzophenone UV absorbers 2-hydroxybenzophenone-based UV absorbers are preferred, and 2'-hydroxyphenyl-5-chlorobenzotriazole-based UV absorbers and 2,2'-dihydroxybenzophenone-based UV absorbers are particularly excellent. It is preferable because it exhibits ultraviolet blocking effect and transparency. The amount of the ultraviolet absorber added to the vinyl chloride resin is preferably 350 mμ or less, more preferably 380 mμ or less, considering the weather resistance, anti-fading properties, etc. of the vinyl chloride resin film and the thickness of these films. It is preferable that the amount is such that it substantially blocks ultraviolet rays having the following wavelengths. “substantial” here
means that 70% or more of ultraviolet rays with a wavelength of 350 mμ,
This means blocking preferably 90% or more, more preferably 95% or more, and such blocking effect is usually achieved by blocking 100 parts by weight of vinyl chloride resin.
This can be achieved with 0.3 to 3 parts by weight, preferably 0.5 to 2 parts by weight. When the amount of the ultraviolet absorber added is 0.3 to 3 parts by weight, the long-term adhesive strength of the fluororesin coating film applied to the vinyl chloride resin film, as well as the adhesive strength of the coating on wood, aluminum plates, iron plates, etc. When the super weather-resistant film according to the present invention is composited onto a coating such as a building material, the long-term strong adhesive strength with the vinyl chloride resin film and the transparency of the film are particularly preferably maintained. Therefore, by adding an ultraviolet absorber, if the coating is printed with, for example, a high-grade wood grain, or if the vinyl chloride resin is in contact with the fluororesin coating layer according to the present invention. When the wood grain printing or the like is applied to the film surface opposite to the film surface, there is an advantage that the printing is prevented from fading and its sharpness is maintained for a long period of time. The “vinyl chloride resin” used in the present invention is
In addition to vinyl chloride sole resin, monomers copolymerizable with vinyl chloride, such as vinyl acetate, ethylene, proprene, acrylic esters, methacrylic esters, etc., at 40% by weight or less, preferably 30% by weight % or less of vinyl chloride; and resins compatible with 100 parts by weight of these resins, such as ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-chloride Vinyl copolymer resins, propylene-vinyl chloride copolymer resins, ethylene-propylene-vinyl chloride copolymer resins (these copolymer resins include graft copolymer resins), etc.
It refers to a resin blended with 30 parts by weight or less, preferably 20 parts by weight or less. These compatible resins include ethylene-vinyl acetate copolymer resin (hereinafter sometimes abbreviated as EVA resin), which has a vinyl acetate content due to its compatibility with the ultraviolet absorber.
Particularly preferred is 10 to 50% by weight. The vinyl chloride resin used in the present invention described below can be processed into a film by any known processing method such as extrusion, melt processing such as calendering, or casting using a solvent or the like. However, tetrahydrofuran, MEK, acetone, benzene,
A solution casting method using an organic solvent such as toluene is preferred. The thickness of the "film" in the present invention is not particularly limited, but it is preferably 15 to 250 microns, more preferably 20 to 150 microns, and particularly preferably 30 to 100 microns. The vinyl chloride resin film according to the present invention can be bonded to a coating such as an aluminum plate as a super weather-resistant film in the form of a solvent-based fluorocarbon resin coating. Furthermore, in order to improve workability such as preventing cracking and whitening of the film when bending the ultra-weather-resistant film composite plate, for 100 parts by weight of vinyl chloride resin,
General plasticizers, preferably polymeric plasticizers 5-
It is preferable to use a vinyl chloride resin film containing 40 parts by weight, more preferably 10 to 30 parts by weight, particularly preferably 10 to 25 parts by weight. The above-mentioned polymeric plasticizer in the present invention has a molecular weight of 800 or more, preferably 900 or more, particularly preferably
950 or more, an epoxy derivative plasticizer or/and a polymeric plasticizer, as such a plasticizer,
As for the epoxy derivative plasticizer, for example, Adeka Sizer, 0-
130P, 0-180A; Sunsocizer E-2000, E-9000 manufactured by Shin Nippon Rika Co., Ltd.; Chitsocizer EPO manufactured by Chitsso Corporation; manufactured by Rohm and Hatsus Co., Ltd.
Paraplex, G-60, G-61, G-62; etc., and polymeric plasticizers, that is, generally dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, etc. As the dihydric alcohol, glycols (especially mono-, di-, tri-ethylene glycol; mono-, di-propylene glycol, etc.) are used, for example, Adeka Sizer, manufactured by Adeka Argus Chemical Co., Ltd. P-200, P-300, PN-150, PN-220,
PN-280, PN-350, PN-400; Polycizer series manufactured by Dainippon Ink & Chemicals Co., Ltd.; Daihachi Chemical
BAA-15 manufactured by Shin Nippon Chemical Co., Ltd.; Sunsocizer, P-2600, P-1500, manufactured by Shin Nippon Chemical Co., Ltd.; Paraplex, G-25, G-40, manufactured by Rohm and Hats Co., Ltd.
Examples include G-50, G-54; Rheoplex 100, 110, 220, manufactured by Ciba Geigy. In addition, if desired, the vinyl chloride resin film according to the present invention may include, for example, phthalic acid derivatives other than the above-mentioned polymers, trimellitic acid derivatives,
Plasticizers such as phosphoric acid derivatives and paraffin derivatives; Stabilizers such as metal soaps, organic tin compounds, pasty composite stabilizers, inorganic acid salts, powder composite stabilizers; fatty acid amides, fatty acids, paraffin and hydrocarbon resins, fatty acid esters , fatty alcohols, fatty acid ketones, partial esters of fatty acids and polyhydric alcohols; inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, carbon black, and other organic pigments such as organic fluorescent pigments; antimony oxide,
Flame retardants such as aluminum hydroxide and halogen-containing phosphate esters can also be used as appropriate. The method of applying the solvent-type fluororesin onto the vinyl chloride film used in the present invention is not particularly limited, and any method can be used depending on the purpose. Specifically, there are two methods: applying a solvent-based fluorocarbon resin directly onto a vinyl chloride film, and applying a solvent-based fluorocarbon resin after pre-priming the vinyl chloride film. In order to obtain further improved adhesive strength between the film and the solvent-based fluororesin, it is preferable to pre-treat the vinyl chloride film with a primer. When applying a solvent-type fluororesin directly onto vinyl chloride film, examples of solvents for the fluororesin include ketones such as MEK and MIBK, esters such as methyl acetate, ethyl acetate, and butyl acetate, and toluene. By using aromatic compounds such as , xylene, other mineral spirits, general organic solvents such as butyl alcohol alone or in combination, it is possible to strongly adhere the vinyl chloride film and the fluororesin. In addition, when applying a solvent-based fluororesin to vinyl chloride film after pre-priming, examples of primers that can be used include acrylic copolymers, polymethyl methacrylate grafted onto natural rubber, and chloroprene. Examples include methyl methacrylate grafted onto nitrile rubber, nitrile rubber-polymethyl methacrylate, natural rubber-polyacrylonitrile, and ethylene/propylene rubber-vinyl monomer. In addition, in order to obtain improved adhesive strength between the ultra-weather-resistant film of the present invention and adherends such as aluminum plates and steel plates, it is necessary to combine butadiene and acrylonitrile, which are known as acrylic copolymers and nitrile rubber (NBR). Examples include copolymer resins such as phenolic, NBR, thermoplastic, epoxy, epoxy-polyamide, and vinyl-epoxy. There is no problem in performing surface normalization treatment, surface roughening treatment, etching treatment, chromate treatment, etc. Hereinafter, a more detailed explanation will be given with reference examples, examples, and comparative examples. Although a solution-casting film is mentioned as the vinyl chloride resin film, the present invention is not limited to these solution-casting films. Reference example 1 (Preparation of vinyl chloride resin film) Vinyl chloride resin [SG-1100, manufactured by Ryoichi Co., Ltd.] 95% by weight and EVA resin [manufactured by Bayer, Levaprene]
450] 100 parts by weight of a vinyl chloride resin consisting of 5% by weight, 5 parts by weight of an epoxy derivative plasticizer [Adeka Sizer 0-130P manufactured by Adeka Argus Chemical Co., Ltd.] and a polymeric plasticizer [Adeka Argus Chemical Co., Ltd.] Kagaku Co., Ltd.
Adeka Sizer PN-400, manufactured by Adeka Argus Chemical Co., Ltd., a total of 20 parts by weight of a polymeric plasticizer consisting of 15 parts by weight, a barium-zinc stabilizer [manufactured by Adeka Argus Chemical Co., Ltd., mark
AC-153] 1 part by weight, ultraviolet absorber [Ciba Gaiki Co., Ltd., Tinuvin 327] 1.2 parts by weight, lubricant [Lion Akzo Co., Ltd., Aramide 0] 0.3 parts by weight, and as a solvent, tetrahydrofuran 450 parts by weight. A mixed solvent consisting of and 50 parts by weight of toluene was added. These mixtures were heated and dissolved in an autoclave at 95°C with stirring, then cooled to about 60°C, defoamed, and the resulting solution was placed on a stainless steel plate using an applicator to obtain a film with a thickness of 50μ. The mixture was cast and dried at about 60°C for 1 hour to prepare a vinyl chloride resin film. Example 1 (Creation of ultra-weather-resistant film) A polymethyl methacrylate primer was applied to the vinyl chloride resin film obtained in Reference Example 1 to a thickness of about 3μ, and the film was heated at a temperature of about 30°C. and dried for 10 minutes. Next, the solid content of the solvent-based fluororesin was 50% by weight, and the solvent was MIBK/xylene = 50/50.
A low-temperature crosslinkable solvent-type fluorine-based resin [Lumiflon LF-302D, manufactured by Asahi Glass Co., Ltd.], in which 10 parts by weight of a crosslinking agent (Coronate EH, manufactured by Nippon Polyurethane Co., Ltd.) is added to 100 parts by weight of the solution, was added to the above film. thickness on top
It was applied using an applicator to a thickness of 10 μm, dried at 60° C. for 1 hour, and then left at room temperature for 7 days to obtain a super weather-resistant film. Example 2 The vinyl chloride resin film obtained in Reference Example 1 was printed with high-quality wood grain, and then treated with a primer in the same manner as in Example 1, and coated with a low-temperature crosslinkable solvent-based fluorocarbon resin to obtain a film that was superior to that of Example 2. A weather-resistant film was obtained. In addition, high-quality wood grain printing is gravure printing of a high-quality wood grain pattern using acrylic resin printing ink on the side of the vinyl chloride resin film that is opposite to the low-temperature crosslinkable solvent-type fluorocarbon resin coating that is formed. This is what I did. In the weather resistance test as a performance test of the super weather resistant films of Examples 1 and 2, they were pasted on an aluminum plate (thickness 2 mm) that had been previously treated with alodine and coated with an epoxy-urethane adhesive, and the upper layer was A synthetic resin-coated aluminum plate with a low-temperature crosslinkable solvent-type fluororesin coating and an aluminum plate as the bottom layer was used as a test material. Including the type of base film of the super weather-resistant films of Examples 1 and 2 above, the presence or absence of high-grade wood grain printing, the presence or absence of primer treatment, the thickness of the solvent-based fluorocarbon resin coating, and the weather resistance test results. Shown in Table 1. () Weather resistance test (1) Sunshine Weather-Ometer An accelerated exposure test was conducted using a Sunshine Weather-Ometer in accordance with JIS A1415, and the materials were evaluated after 10,000 hours had elapsed. The test conditions used a sample with dimensions of 150 mm x 70 mm.
The black panel temperature was 65° C., the spray water cycle was 18 minutes out of 180 minutes, the spray water pressure was 1 Kg/cm ² , and ion-exchanged water was used as the spray water. (2) Ematsuka Test (Solar Accumulated Outdoor Accelerated Weather Resistance Test) After being conducted for two years in the Arizona desert in the United States, evaluation was conducted (sample dimensions were 300 mm x 300 mm). The total light dose during the test period was 2 million Langreis. () Evaluation All samples were evaluated after the weather resistance test was completed. (1) Color difference △E*ab Measured according to the object color measurement method specified in JIS Z8722, and displayed △E*ab based on the color difference display method of JIS Z8730. Measuring equipment: Nippon Denshoku Co., Ltd. colorimeter model Z-
Measured with 1001DP. (2) Gloss retention rate (%) Measured using the 60 degree specular gloss measurement method specified in JIS K5400, with the gloss level before the weather resistance test as 100%.
The gloss retention rate after the weather resistance test was expressed in %. (3) Adhesive strength The peel test was conducted in accordance with JIS K6744. The obtained peeling load was evaluated in five stages as follows. #5 3.0Kgf/20mm or more #4 2.5~3.0Kgf/20mm #3 2.0~2.5Kgf/20mm #2 1.0~2.0Kgf/20mm #1 0~1.0Kgf/20mm Comparative Examples 1~5 Comparative Examples 1~2 , Comparative Example 3 used the vinyl chloride resin film of Reference Example 1, no ultraviolet absorber was added, and Comparative Examples 4 and 5 used a 50μ thick vinyl fluoride resin film and vinylidene fluoride film. , based on the methods described in Examples 1 and 2 under various conditions as shown in Table 1, and tested based on the weather resistance test described above.
The results of these tests are also shown in Table 1. As can be seen from Table 1, the super weather-resistant film of Example 2 of the present invention exhibits similar properties to the fluororesin films of Comparative Examples 4 and 5, and the super weather-resistant film of Example 2 tested as a coated aluminum plate. It also showed excellent adhesive strength. Incidentally, it was difficult to apply high-grade wood grain printing to fluororesin and use it as a test sample. 【table】

Claims (1)

[Scope of Claims] 1. A super weather-resistant film comprising a vinyl chloride resin film containing an ultraviolet absorber and coated with a solvent-type fluororesin. 2. The super weather resistant film according to claim 1, wherein the fluororesin is crosslinkable at low temperatures. 3. The super weather-resistant film according to claim 1 or 2, wherein the ultraviolet absorber is benzotriazole-based and/or benzophenone-based. 4 The vinyl chloride resin film contains 5 to 40 parts by weight of a polymer plasticizer per 100 parts by weight of the vinyl chloride resin.
Claims 1 to 2 contain parts by weight.
The ultra-weather-resistant film according to any one of item 3. 5. The super weather-resistant film according to any one of claims 1 to 4, wherein the vinyl chloride resin film substantially blocks wavelengths of 350 mμ or less. 6. The super weather resistant film according to any one of claims 1 to 5, wherein the vinyl chloride resin film is produced by a solution casting method.