JPH0224140A - Weather resistant structure - Google Patents

Abstract

PURPOSE:To prevent a base from discoloring and property-deteriorating by suppressing the transmission of ultraviolet ray, while the excellent properties such as the weather resistance, etc., of PVdF if not reduced by laminating a vinylidene fluoride resin layer on at least one surface of a base through the acrylresin layer containing an ultraviolet-ray absorbent. CONSTITUTION:A PVdF resin layer is laminated on one surface or both surfaces of a base through an acrylresin layer, whereby the protecting layer with weathering resistance is formed. The acrylresin layer has the main component of acrylresin and contains an ultraviolet-ray absorbent. As the ultraviolet-ray absorbent contained in acrylresin, the ultraviolet-ray absorbents such as benzotriazole, monohydroxybenzophenone, dihydroxybenzophenone, salicylate and benzoate, etc., are used. The content of the ultraviolet-ray absorbent in the acrylresin layer is preferably 0.1-5wt.%. A vinylidene fluoride resin layer is composed of vinylidene fluoride resin which is the copolymer of single vinylidene fluoride or monomer mixture containing vinylidene fluoride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a weather-resistant structure, and particularly to a weather-resistant structure that does not discolor due to ultraviolet rays or deteriorate physical properties such as brittleness, bending strength, and elongation.

[Conventional technology]

The surface of the base material is coated with polyvinylidene fluoride (
Conventionally, it has been carried out to improve the weather resistance of a substrate by coating it with (hereinafter sometimes abbreviated as r PVdF J).

However, although PVdF has good weather resistance, it is highly transparent to ultraviolet rays, so ultraviolet rays that pass through the PVdF layer are absorbed by the base material, causing discoloration of the base material and deterioration of physical properties such as brittleness, bending strength, and elongation. There was a problem with the cause.

Therefore, a method has been proposed in which an ultraviolet absorber is added to PVdF to prevent the transmission of ultraviolet rays. However, most UV absorbers have no affinity with PVdF, and there are problems such as the added UV absorber migrating to the surface of the PVdF layer. Absorbents have little effect on improving weather resistance and are not practical.

Therefore, in order to improve the affinity between PVdF and the ultraviolet absorber, PVdF has been proposed that further contains an acrylic resin that has good affinity for both PVdP and the ultraviolet absorber.

[Problem to be solved by the invention]

However, PVdF mixed with an acrylic resin has problems such as the weather resistance of the surface of the resulting PVdF layer being several orders of magnitude inferior to that of PVdF alone, and poor stain resistance. Furthermore, in order to improve the affinity between PVdF and the ultraviolet absorber, it is necessary to add a large amount of acrylic resin, which poses the problem of lowering the heat resistance.

Therefore, an object of the present invention is to provide a weather-resistant structure that can prevent the transmission of ultraviolet rays and prevent discoloration and deterioration of physical properties of the base material without impairing the excellent properties of PVdF such as weather resistance. It is about providing.

[Means for Solving the Problems] The present invention solves the above problems by forming a vinylidene fluoride resin layer on at least one side of a base material via a (meth)acrylic resin layer containing an ultraviolet absorber. The present invention provides a weather-resistant structure made of laminated layers.

The weather-resistant structure of the present invention has a PVdF resin layer laminated on at least one side of a base material, that is, on one or both sides of the base material, with an acrylic resin layer interposed therebetween to form a weather-resistant protective layer. It is something.

The base material in the structure of the present invention is not particularly limited, and may be in various shapes such as a plate shape, a film shape, a woven fabric, a nonwoven fabric, or a suitably formed material thereof, and the material may be There are also no particular limitations on synthetic resins such as vinyl chloride resins, ABS resins, acrylic resins, cellulose resins, polycarbonate resins, polyester resins, urethane resins, natural materials such as wood, or processing thereof. It may be made of paper, cloth, plywood, etc. Furthermore, it may have a pattern, printing, etc. on its surface.

The vinylidene fluoride resin layer of the structure of the present invention is made of a vinylidene fluoride resin that is a polymer of vinylidene fluoride alone or a monomer mixture containing vinylidene fluoride. The monomer mixture containing vinylidene fluoride contains vinylidene fluoride and another monomer copolymerizable with vinylidene fluoride. Examples of other monomers copolymerizable with vinylidene fluoride include fluorine-based monomers such as tetrachloroethylene, chlorotrifluoroethylene, vinyl fluoride, and hexafluoropropylene. One or more types of these other monomers may be included. Usually, these other monomers may be contained in the vinylidene fluoride resin in an amount of about 20 weight or less.

The (meth)acrylic resin layer of the structure of the present invention has (meth)acrylic resin as a main component and contains an ultraviolet absorber. This (meth)acrylic resin includes, for example, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, etc. One or more polymers of (meth)acrylic acid monomers, or their (meth)
It may also be a copolymer of an acrylic acid monomer and another monomer copolymerizable with the acrylic acid monomer. Examples of the other monomers that can be copolymerized include ethylene, styrene, etc., and even if one or more of these other monomers are contained in the (meth)acrylic resin, good. Usually, these other monomers may be contained in the (meth)acrylic resin in an amount of about 20 weight or less.

The ultraviolet absorber contained in (meth)acrylic resin is
There are no particular limitations, and examples include benzotriazole-based, monohydroxybenzophenone-based, dihydroxyhensiphenone-based, salicylic acid ester-based, and benzoate-based ultraviolet absorbers. More specifically, as a commercially available product, Tinuvin #234 manufactured by Ciba Geigy
, Tinuvin P; manufactured by American Cyanamid Company, Sheasorb 1 No. 9, Sheasorb UV-24i manufactured by Istman Chemical Company, Inhibitor RMB, manufactured by Dow Chemical Company, and Salol.

The content of these ultraviolet absorbers in the (meth)acrylic resin layer is usually preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight.

If the content of the ultraviolet absorber is too low, the effect of improving weather resistance in the resulting structure will be small, and in order to obtain the desired weather resistance, the (meth)acrylic resin layer will have to be thickened, which will increase the cost. Along with causing the rise (meta)
The properties of the acrylic resin layer may become stronger and the physical properties of the PVdF and the base material may be impaired.

The (meth)acrylic resin layer containing the ultraviolet absorber of the structure of the present invention is usually formed on the base material with a thickness of 1 to 100 μm, preferably 5 to 20 μm. If the (meth)acrylic resin layer is too thin, the effect of improving weather resistance in the resulting structure will be small (in order to obtain the desired weather resistance, a large amount of ultraviolet absorber must be included, (There is a risk that the properties of the (meth)acrylic resin layer will become stronger, impairing the physical properties of PVdF and the base material, and the adhesive strength may become weak.) .

The method for producing the structure of the present invention is not particularly limited, and includes, for example: (1) Dissolving the ultraviolet absorber and (meth)acrylic resin in an appropriate solvent to form a solution, and applying this solution to a vinylidene fluoride resin film. , a method of drying to produce a film having a (meth)acrylic resin layer on one side, and applying this film to a substrate.

■A film made of (meth)acrylic resin containing an ultraviolet absorber and a vinylidene fluoride resin film are separately produced, and the (meth)acrylic resin film and vinylidene fluoride resin film are coated on the surface of the base material. A method in which they are stacked one on top of the other, then heated and pressure-molded to form a single piece.

■ A (meth)acrylic resin containing an ultraviolet absorber is dissolved in an appropriate solvent to form a solution, and this solution is applied to a base material and dried to form a (meth)acrylic resin layer. Layer vinylidene fluoride resin and heat.
This can be done by a method such as a method of forming by applying pressure. The heating and pressurizing methods include the methods used for normal film lamination, such as the continuous roll press method using a combination of heating rolls and rubber rolls, the heating and pressing method using a flat plate press, and the heating method using a combination of rolls and belts. Examples include pressurization method. The temperature of the heat treatment is usually 80°C.
In the case of the roll method, the pressure of ~200°C1 is usually
1~10kg/c+fl, 5~50k with flat plate press method
It is a g/c ship. When forming a (meth)acrylic resin layer by applying a solution of (meth)acrylic resin, examples of solvents for preparing the solution include toluene, methyl ethyl ketone, xylene, methyl isobutyl ketone,
Examples include n-hexane and cellosolve ester. These solvents may be used alone or in combination.

Furthermore, in manufacturing the structure of the present invention, if one side of the vinylidene fluoride resin layer is previously subjected to low-temperature plasma treatment and then a (meth)acrylic resin layer is formed on this one side, the (meth)acrylic resin in the structure Adhesion between the layer and the vinylidene fluoride resin layer can be improved. This low-temperature plasma treatment is performed, for example, in an argon gas atmosphere under a pressure of 0.6 Torr, a frequency of 110 kllz, a discharge power density of 6 W/ci, and a total discharge treatment power of 40 W/sec.
This can be done with cTil.

In manufacturing the structure of the present invention, a structure having a matte surface can be obtained by subjecting the surface of the film forming the vinylidene fluoride resin layer to a matte treatment. For example, when producing a vinylidene fluoride film, the matting treatment can be carried out by: ■ casting molten vinylidene fluoride onto a matting roll, ■ physically treating the surface of the film with sandblasting, etc., ■ amorphous silica, The temperature at which the vinylidene fluoride film is sufficiently softened, for example, by a method of adding and mixing an inorganic filler such as calcium carbonate, white carbon, talc, or titanium oxide, or when coating a base material with a vinylidene fluoride film, is 200°C. °C
Examples include a method in which heat and pressure treatment is performed using a laminating roll having a matte surface at a certain temperature.

The weather-resistant structure of the present invention can be applied, for example, to wallpaper, decorative paper such as advertising paper, printed plywood, fabric for tents, plastic boards for signboards, exterior walls of terrace carports, roofing materials, exterior materials for buildings, etc. .

(Examples) Hereinafter, the present invention will be explained in detail by giving Examples and Comparative Examples.

Example 1 (1) Using an extruder, polyvinylidene fluoride (manufactured by Trubay Co., Ltd., Solef 100B) was extruded from a T-die at 250°C and taken off onto a cooling roll to a thickness of 0.025 mm. +++m width 500
A film of mm was produced.

When the light transmittance of the obtained film was measured, it was 92.
%Met. When this film was laminated onto plywood with a pattern on its surface, the pattern on the plywood could be completely seen through the film.

Polymethyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd.)
Acrivet MD) was dissolved in toluene to obtain a clear and viscous liquid with a concentration of 25%.

A UV absorber (Tinuvin #234, manufactured by Ciba Geigy) was mixed and dissolved in the resulting liquid to a concentration of 2% to prepare a (meth)acrylic resin solution containing the UV absorber.

(3) Containing the ultraviolet absorber prepared in (2) (
A meth)acrylic resin solution was applied to one side of the vinylidene fluoride film produced in (1) using a knife coater.
Coated to a thickness of 0.05 mm and dried to a thickness of 0.012 m.
A vinylidene fluoride resin film having m (meth)acrylic resin layer on one side was obtained.

The (meth)acrylic resin layer formed on one side of the obtained film had no stickiness at room temperature after drying and could be rolled up. In addition, this film has a light transmittance of 95% due to the improved smoothness of the (meth)acrylic resin layer.
improved.

(4) Polyvinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK
-700) 0.5 parts by weight of dibutyltin malate and 1.0 parts by weight of epoxidized soybean oil as a 100-weight stabilizer and 0.3 parts by weight of stearic acid as a lubricant were mixed, and the mixture was mixed using an extruder. A transparent polyvinyl chloride resin film having a thickness of 0.5 mm was produced by extruding it from a T-die at 190°C and taking it on a cooling roll.

(5) Fullum's polyvinyl chloride resin film obtained in 1 (4) and (3)
) was stacked with the vinylidene fluoride resin film having the (meth)acrylic resin layer on one side, with the (meth)acrylic resin layer in between, and then heated between pressure rolls heated to 150°C. was passed through the film at a passing speed of 10 m/min to obtain a weather-resistant film.

In the resulting weather-resistant film, the polyvinyl chloride resin film and the vinylidene fluoride resin film were firmly adhered to each other via the (meth)acrylic resin layer, and the film became integral in appearance. Also, regarding this weather-resistant film,
A weather resistance test was conducted using a Sunshine Weather Meter (manufactured by Suga Test Instruments). The degree of coloring is made by Nippon Heavy Industries Co., Ltd.
It is indicated by the E value measured by a color meter. The results are shown in Table 1.

Comparative Example 1 A film was produced in the same manner as in Example 1, except that no ultraviolet absorber was added to the (meth)acrylic resin solution in (2) of Example 1, and subjected to a weather resistance test. The results are shown in Table 1.

Comparative Example 2 The polyvinyl chloride resin film obtained in (4) of Example 1 was subjected to a weather resistance test. The results are shown in Table 1.

Example 2 (1) A ru mail 1 ru, 1
5 films of polymethyl methacrylate resin (manufactured by Mitsubishi Rayon ■, Akrivera MD) was mixed with a UV absorber (Tinuvin #235, manufactured by Ciba Geigy) at a ratio of 2%, and was It was extruded at C and taken up on a cooling roll to produce a film with a thickness of 0.01 mm.

(2) Polyvinyl chloride resin from Bo1 Vinyl Flume (manufactured by Shin-Etsu Chemical Co., Ltd., TK
-1000) 100 parts by weight, plasticizer (DOP) 30
Parts by weight, 1 part by weight of barium stearate and 0.3 parts by weight of zinc stearate as stabilizers, and 1 part by weight of pigment (titanium oxide) were mixed and kneaded at 160°C using a mixing roll. . After that, reverse type 4
It was rolled into a film at 180°C using this calendar and taken up on a cooling roll to obtain a white film with a thickness of 0.3 mm.

(3) The (meth)acrylic resin film and polyvinyl chloride resin film produced in (1) and (2), and the vinylidene fluoride resin film produced in (1) of Example 1, were The resin films were placed one on top of the other, and passed between a metal roll and a rubber roll heated to 150°C, heated and pressurized, and molded into one piece.

The obtained molded product was a white film in which a transparent vinylidene fluoride resin layer was formed on the surface of a polyvinyl chloride resin via a (meth)acrylic resin layer containing an ultraviolet absorber. This film was subjected to a weather resistance test in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 The polyvinyl chloride resin film produced in Example 2 (2) was subjected to a weather resistance test in the same manner as in Example 1.

The results are shown in Table 1.

Example 3 The (meth)acrylic resin solution prepared in Example 1 (2) was applied to the vinylidene fluoride resin film prepared in Example 1 (1) using a reverse roll coater to a thickness of 0.
．． It was applied to 02mm. After drying in a ventilation drying room, 1
Heating using a laminating roll heated to 50°C,
By applying pressure, a vinylidene fluoride resin layer was formed on the surface of the wallpaper printing paper via a (meth)acrylic resin layer.

Example 4 One side of the vinylidene fluoride resin film produced in (1) of Example 1 was heated to a pressure of 0.4 T in an argon gas atmosphere.
orr, peak voltage between electrodes 5000 V, discharge power density 8.8 W/cd, total discharge processing power 32 W sec/c
Low-temperature plasma treatment was performed under the conditions of 4. Next, as in Example 3, the ultraviolet absorber prepared in (2) of Example 1 was applied to the low-temperature plasma-treated surface of the film (meth).
An acrylic resin solution was applied to form a (meth)acrylic resin layer.

The peeling force between the (meth)acrylic resin layer and the vinylidene fluoride resin layer in the obtained film was more than twice that of the film obtained in Example 1. Moreover, the weather resistance was comparable to that of Example 1.

Example 5 Instead of the vinylidene fluoride resin film in Example 2, a film obtained by subjecting one side of the vinylidene fluoride resin film to low-temperature plasma treatment in the same manner as in Example 4 was used, and this plasma-treated A (meth)acrylic resin film was superimposed on the surface, and a polyvinyl chloride resin film was further superimposed on the (meth)acrylic resin film to perform laminate molding.

The peeling force between the (meth)acrylic resin layer and the vinylidene fluoride resin layer of the obtained film was greater than that of the film obtained in Example 1, and the improvement in adhesive strength was remarkable.

[Effects of the Invention] The weather-resistant structure of the present invention not only has the excellent weather resistance of PVdF, but also prevents the base material from absorbing ultraviolet rays by the ultraviolet absorber contained in the (meth)acrylic resin layer. There is no discoloration of the base material or deterioration of physical properties due to ultraviolet rays. For example, even in an environment where it is exposed to ultraviolet light for a long period of time, it does not change color and can maintain its initial color. Furthermore, in the case of structures used outdoors, such as tents, it is possible to prevent discoloration due to ultraviolet rays and to prevent strength deterioration. In addition, PVdF and (
Since both meth)acrylic resins are colorless and transparent, printing, decoration, etc. applied to the base material can be maintained.

Agent Patent Attorney Comrade Iwamiya Proceedings (Hoshosho (spontaneous) September 30, 1985 1, Indication of the case 1988 Patent Application No. 174300 2, Name of the invention Weatherproof structure 3, Person making the amendment Relationship to the incident Patent applicant address: 2-6-1 Otemachi, Chiyoda-ku, Tokyo Name
(206) Shin-Etsu Chemical Co., Ltd. 4, Agent address: 1-26 Kanda Jimbocho, Chiyoda-ku, Tokyo 101
Number of inventions increased by amendment None 7. Subject of amendment Detailed explanation of the invention in the specification column 8, Contents of amendment (1) ", ■
"Method of adding and mixing amorphous silica and calcium carbonate" is deleted.

Procedural amendment ([1 button ■, Indication of the case, Patent Application No. 174300 of 1988 2, Name of the invention Weatherproof structure 3, Person making the amendment Relationship to the case Patent applicant address 2 Otemachi, Chiyoda-ku, Tokyo Chome 6-1 Name (2
06) Shin-Etsu Chemical Co., Ltd. 4, Agent address: 1-2-3 Kanda Jimbocho, Chiyoda-ku, Tokyo 101 Date of amendment order Number of claims increased by voluntary amendment None Subject of amendment
Contents of amendment in the Detailed Description of the Invention section of the specification (1) The description of "Tinuvin #235°" on page 14, line 3 of the specification is amended to r-Tinuvin #234J.

Otsu

Claims (1)

[Claims] A weather-resistant structure formed by laminating a vinylidene fluoride resin layer on at least one side of a base material with a (meth)acrylic resin layer containing an ultraviolet absorber interposed therebetween.