JPS6134390B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composite reinforced plastic board in which a polyvinyl fluoride film is bonded to a glass fiber-reinforced unsaturated polyester resin layer, and a method for manufacturing the same. The object of the present invention is to provide a composite reinforced plastic board that has high adhesive strength between the materials and has excellent properties such as transparency and weather resistance, especially weather resistance related to yellowing resistance, and a method for producing the same. Conventionally, glass fiber-reinforced unsaturated polyester resin (hereinafter referred to as FRP) plates, which are made by integrally curing and molding unsaturated polyester resin and glass fiber, are often manufactured as corrugated plates or flat plates with excellent transparency. ing. The unsaturated polyester resin used to manufacture this FRP board is generally obtained by diluting an unsaturated polyester prepolymer obtained by reacting maleic anhydride or phthalic anhydride with ethylene glycol, etc., with styrene or methyl methacrylate. Yes, FRP obtained by impregnating glass fiber with such unsaturated polyester resin and curing it.
The board had drawbacks such as yellowing and resin thinning due to long-term outdoor exposure. This yellowing tendency is particularly noticeable in FRP boards made of flame-retardant unsaturated polyester resins that contain chlorine-containing hectate (chlorent acid), organic phosphates, brominated phthalic acid, etc. as acid components. Significant. In order to eliminate the yellowing phenomenon of FRP boards, a polyfluorinated vinyl film whose surface has been oxidized by corona discharge is bonded directly to the surface of the FRP board to create a polyfluorinated vinyl film laminate FRP board. It hardly yellows or loses its resin even after long-term outdoor exposure, and is used as FRP board especially in fields where weather resistance is required. However, in this polyfluorinated vinyl film laminate FRP board, the polyfluorinated vinyl film that functions as a protective film has poor adhesive properties, and the surface of the polyfluorinated vinyl film is oxidized by corona discharge to improve adhesiveness. However, the adhesion to the FRP layer was insufficient, and over time the polyvinyl film and FRP
Partial peeling occurs between the layers, which not only deteriorates the appearance, but also causes yellowing and thinning of the resin in the peeled portions of the FRP layer, which has the disadvantage of greatly reducing commercial value. As a result of various studies on the causes of the above-mentioned peeling, the inventors of the present invention found that the heat shrinkage of the polyvinyl fluoride film is a major factor that influences the adhesiveness between the polyfluorinated vinyl film and FRP, in other words, the peelability. Although it was found that the surface properties and the degree of curing of the unsaturated polyester resin were improved, it was found that improving these factors alone would not cause the partial peeling phenomenon between the polyfluorinated vinyl film and the FRP layer. We found that it is impossible to completely prevent this. As a result of intensive research into adhesives having suitable adhesion ability, which influences adhesiveness most significantly among the above factors, the present inventors have found that the function of the protective film can be improved by adopting the structure described in the claims. The adhesive strength between the polyfluoride vinyl film and the unsaturated polyester resin, etc. in the FRP layer is extremely high, and there is no risk of the polyfluoride vinyl film peeling off even after long-term outdoor exposure, making it transparent. Thus, we have been able to provide a composite reinforced plastic board with excellent weather resistance, particularly weather resistance related to yellowing resistance, and a method for producing the same. As illustrated in FIG. 1, the composite reinforced plastic board of the present invention has a polyvinyl fluoride film layer 3 provided on the surface of a glass fiber reinforced unsaturated polyester resin layer 1 via an adhesive layer 2, The fiber-reinforced unsaturated polyester layer 1, the adhesive layer 2, and the polyfluorinated vinyl film layer 3 are integrally bonded and fixed, and the adhesive layer 2 is made of a bisphenol-based unsaturated polyester resin, It contains one or more synthetic resins selected from vinyl ester resins or oligoester acrylate resins as a resin component, and the glass fiber reinforced unsaturated polyester resin layer 1 and the adhesive layer The curable synthetic resin component in 2 is cured, and the glass fiber reinforced unsaturated polyester layer 1 and polyfluorinated vinyl film layer 3 are each firmly and integrally fixed to the adhesive layer 2. be. The composite reinforced plastic board of the present invention having the structure as illustrated in FIG. An adhesive containing one or more synthetic resins as a resin component is usually applied to a thickness of about 10 to 40μ, and then heated to about 50 to 100℃ or irradiated with an ultraviolet lamp. A mixed composition of the polyfluorinated vinyl film obtained by pre-curing the polyvinyl fluoride film, an unsaturated polyester resin and glass fibers, that is, a glass fiber mat impregnated with the unsaturated polyester resin, or a glass fiber mat is immersed. A certain unsaturated polyester resin or the like is laminated such that the adhesive coated surface of the polyvinyl fluoride film is in contact with the surface of the mixed composition of the unsaturated polyester resin and glass fiber, and more specifically, An unsaturated polyester resin-impregnated glass fiber mat or the like is placed between a predetermined polyfluorinated vinyl film and an intervening film such as cellophane, vinylon, or nylon film so that the adhesive-coated surface of the polyfluorinated vinyl film is unsaturated. A sandwich structure is made by sandwiching the polyester resin-impregnated glass fiber mat in contact with the surface, and this is passed through a heating furnace at about 80 to 150 degrees Celsius to harden the unsaturated polyester resin in the glass fibers, and also to cure the adhesive. It consists of completely curing the curable resin inside. In the present invention, ordinary E-glass chopped strands or continuous filaments can be used as the glass fibers of the glass fiber-reinforced unsaturated polyester resin layer, but the resulting composite reinforced plastic board has transparency. It is desirable to use glass fiber with a refractive index of 1.54 to 1.55. In addition, unsaturated polyester resins have unsaturated acids such as maleic acid, fumaric acid, citraconic acid,
Itaconic acid, etc. Saturated acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, hexahydrophthalic anhydride, brominated phthalic acid, hexic acid, etc. Glycols include ethylene glycol, propylene glycol, diethylene glycol , dipropylene glycol,
Constructed from flame-retardant type or general type unsaturated polyester resin obtained by using general vinyl monomers such as styrene and methyl methacrylate as monomer diluents such as neopentyl glycol, triethylene glycol, and trimethylene glycol. I can do it. The ratio of glass fibers and unsaturated polyester resin in this glass fiber-reinforced unsaturated polyester resin layer is determined from the viewpoints of the strength required for the resulting FRP layer and the impregnability of the unsaturated polyester resin itself into the glass fibers. Glass fiber 20~30
It is preferable that the amount of unsaturated polyester resin be about 80 to 70% by weight. The adhesive used in the present invention exhibits extremely strong adhesion to both the polyfluorinated vinyl film and the unsaturated polyester resin in the FRP layer, and contains (1) bisphenol unsaturated resin as the resin component. It contains one or more synthetic resins selected from polyester resins, (2) vinyl ester resins, and (3) oligoester acrylate resins. The synthetic resin contained as an essential resin component in this adhesive will be described in detail below. (1) Bisphenolic unsaturated polyester resin structural formula This resin has a bisphenol skeleton in its main chain, and because the molecular weight of this bisphenol skeleton is large, the ester group concentration is low, making it difficult for hydrolysis to occur. Therefore, it exhibits excellent performance in alkali resistance, acid resistance, and salt resistance. (2) Vinyl ester resin structural formula This resin has an ester group and an acrylic group only at the end. The main chain is a bisphenol skeleton, and does not have repeating ester groups or double bonds in the main chain, unlike bisphenol polyester resins. Therefore, vinyl ester resins can have the lowest ester group concentration, and therefore have better corrosion resistance and solvent resistance than bisphenol polyester resins. (3) Oligoester acrylate resin structural formula This resin is a photopolymerizable resin with an acryloyl group at the end of the molecule. There is an advantage that the physical properties of the produced oligomer can be selected over a wide range by changing the charging ratio of raw materials during synthesis. The adhesive used in the present invention includes the above (1),
It contains one or more synthetic resins selected from (2) and (3) as an essential resin component, but all of the synthetic resins used as essential resin components are expensive. Therefore, for the purpose of reducing costs, a general or flame-retardant type unsaturated polyester resin may be mixed with the above-mentioned essential resin and used. In this case, if the general or flame retardant type unsaturated polyester resin is contained in an amount exceeding 60% by weight of the resin component in the adhesive,
Since the adhesive strength of the adhesive is reduced, it is preferable that the amount of general or flame-retardant unsaturated polyester resin added or mixed is kept to 60% by weight or less based on the resin component of the adhesive. As a curing catalyst for the curable synthetic resin in the adhesive, common organic peroxides such as benzoyl peroxide, cumene hydroperoxide,
2.4 dichlorobenzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide-cobalt naphthenate, t-butyl peroxyneodecanoate, etc. can be used. The amount of curing catalyst to be used is 0.5 parts by weight per 100 parts by weight of the resin component, considering the pot life and curability of the resin component constituting the adhesive, and the weather resistance of the resulting adhesive layer.
It is desirable that the amount is 2 parts by weight. In particular, when ultraviolet irradiation is used as a means of pre-curing adhesives applied to polyfluorinated vinyl films, known sensitizers such as benzoin ethyl ether, benzoin isopropyl ether, methyl orthobenzoyl benzoate are added to the adhesive. , benzyl dimethyl ketal, diethoxyacetophenone, etc. can be added and used. in this case,
The amount of this sensitizer to be used is 0.1 to 1 part by weight per 100 parts by weight of the resin component in the adhesive, taking into account the weather resistance of the resulting adhesive layer and the cost increase due to the addition and use of the sensitizer. It is desirable that the amount be approximately 100%. The specific structure of the composite reinforced plastic board of the present invention and its manufacturing method will be described below with reference to Examples. Example 1 Benzoyl peroxide (50%
paste) and 1 part by weight of bis-4-t-butylcyclohexyl peroxydicarbonate (50% paste) were added, mixed well, defoamed, and mixed into a 25μ thick polyfluorinated vinyl film [DuPont ( Co., Ltd.: Tedora-100BG15UT] to a thickness of about 30 μm, and heated in a dryer at 80° C. for 1 minute. Next, a mold having a height of about 1 mm was placed and fixed on the surface of the obtained polyfluorinated vinyl film coated with the bisphenolic unsaturated polyester resin. After that, 100 parts by weight of a general type of unsaturated polyester resin of the following composition was well mixed and defoamed, and 37 parts by weight of E glass chopped strands [manufactured by Nitto Boseki Co., Ltd.: PU-538] were added to the mixture. A mixed composition of unsaturated polyester resin and glass fiber obtained by adding and mixing ] was injected onto the above-mentioned polyfluorinated vinyl film, and the top surface was covered with cellophane, and the glass fiber content was approx. Extrude the excess resin with a roller to make it 25%, then heat it to 90℃.
After heating for 6 minutes in a dryer, the temperature was further increased to 150°C at a rate of 8°C/min to obtain a composite reinforced plastic plate (A) with a thickness of 1.0 mm, which is an example of the present invention.

[Table] Example 2 1 part by weight of benzoin ethyl ether as a photosensitizer was added to 100 parts by weight of vinyl ester resin [manufactured by Showa Kobunshi Co., Ltd.: Lipoxy R-806DA], mixed and defoamed. 25μ thick polyvinyl vinyl film [manufactured by Dupont Co., Ltd.: Tedlar]
100BG15UT] to a thickness of approximately 30μ, and then irradiated with an ultraviolet lamp with an irradiation energy of 160W/cm for 20 seconds. Thereafter, the same operations as in Example 1 were performed to obtain a sample with a thickness of 1.0, which is an exemplary product of the present invention.
A flat plate (B) of composite reinforced plastic of mm was obtained. Example 3 Oligoester acrylate resin [Toagosei Co., Ltd.]
Manufactured by: Aronix M-8030] 40 parts by weight of a certain general type of unsaturated polyester resin from the following composition 60
In addition, 1 part by weight of benzoyl peroxide (50% paste) as a catalyst and Bis 4
-t-butylcyclohexyl dicarbonate (50
% paste), mix well, defoam, and apply this onto a 25μ thick polyfluoride vinyl film (manufactured by Dupont Co., Ltd.: Tedora-100BG15UT).
After coating to a thickness of 30 μm, it was heated in a dryer at 80° C. for 1 minute. Thereafter, operations were performed in exactly the same manner as in Example 1 to obtain a composite plastic flat plate (C) with a thickness of 1.0 mm, which is an exemplary product of the present invention.

[Table] Example 4 50 parts by weight of the bisphenol polyester resin described in Example 1 and 50 parts by weight of the oligoester acrylate resin described in Example 3 were mixed, and benzoyl peroxide (50% paste) was added as a catalyst. ) 1 part by weight and bis-4-t-butylcyclohexyl peroxydicarbonate (50% paste)
1 part by weight was added, mixed, and defoamed. The obtained resin mixture was applied to a thickness of about 30μ on a 25μ thick polyfluorinated vinyl film (manufactured by Dupont Co., Ltd.: Tedra-100BG15UT), and heated for 1 minute in a dryer at 80°C. did. Thereafter, operations were carried out in exactly the same manner as in Example 1 to obtain a composite plastic flat plate (D) with a thickness of 1.0 mm, which is an exemplary product of the present invention. Example 5 40 parts by weight of the oligoester acrylate resin described in Example 3 was mixed with 60 parts by weight of a flame-retardant unsaturated polyester resin having the composition shown below, and 2 parts by weight of t-butylperoxyneodecanoate were added as a catalyst. Parts by weight were added, mixed, and defoamed. The obtained resin mixture was placed on a 25μ thick polyfluorinated vinyl film [DuPont Co., Ltd.: Tedlar 100BG15UT].
After coating to a thickness of about 30μ, it was heated in a dryer at 80°C for 1 minute. Then, on the surface of the obtained polyfluorinated vinyl film coated with the resin mixture,
A formwork with a height of approximately 1 mm was placed and fixed. Thereafter, 1 part by weight of benzoyl peroxide (50% paste) and cumene hydro as a catalyst were added to 100 parts by weight of an unsaturated polyester resin having the same composition as the flame-retardant unsaturated polyester resin mixed with the oligoester acrylate resin. 1 part by weight of peroxide was added, mixed and defoamed, and 25 parts by weight of E glass chopped strands (manufactured by Nittobo Co., Ltd.: PU-538) were added and mixed. The resulting mixed composition of unsaturated polyester resin and glass fibers was injected onto the above-mentioned polyfluorinated vinyl film, and the subsequent operations were then carried out in exactly the same manner as in Example 1 to obtain an exemplary product of the present invention. Flat plate of composite reinforced plastic with barrel thickness 1.0mm
I got (E).

[Table] Comparative Example 1 To 100 parts by weight of the general type unsaturated polyester resin used in Example 3, 1 part by weight of benzoyl peroxide (50% paste) and bis-4-t-butylcyclohexyl peroxydicarbonate were added as catalysts. (50% paste) and mix well, add this to a thickness of 25μ
It was applied to a thickness of about 30 μm on a polyfluorinated vinyl film (manufactured by Dupont Co., Ltd.: TEDRA-100BG15UT), and heated in a dryer at 80° C. for 1 minute. Thereafter, operations were performed in exactly the same manner as in Example 1 to obtain a composite plastic flat plate (F) with a thickness of 1.0 mm for comparison. Comparative Example 2 A formwork with a height of approximately 1 mm was placed and fixed directly on a polyfluoride vinyl film with a thickness of 25 μm (manufactured by Dupont Co., Ltd.: Tedlar 100BG15UT), and then the above-mentioned method was placed on this polyfluoride vinyl film. The subsequent operations were carried out in exactly the same manner as in Example 1 to obtain a composite plastic plate (G) with a thickness of 1.0 mm for comparison. The composite plastic plates (A) to (G) obtained in the above Examples and Comparative Examples were placed in hot water at 85℃ for 2 hours.
A hot water immersion test in which the sample was immersed for 1 hour, 3 hours, and 7 days, and a heating and pressure test in which the sample was left in an autoclave at 120° C. (3.0 Kg/cm ² ) for 2 hours were conducted, and the peeling state in each test was observed. To observe the peeling state, after the test was completed, a knife was used to make a scratch with a width of about 2 mm and a length of about 10 mm, and the scratched area was peeled off with the edge of the knife. The peeling condition was confirmed. The results are shown in Table 1.

[Table] As a result of outdoor exposure tests conducted on the composite plastics (A) to (G) obtained in the above Examples and Comparative Examples, flat plates (A) to (E) showed no peeling phenomenon even after one year. No growth occurred, and there was no yellowing at all. Flat plates (F) and (G) are 3
During a month-long outdoor exposure test, the polyfluorinated vinyl film on the surface partially peeled off, and striped contamination was observed in this peeled area. In addition, in the flat plates (F) and (G), the polyfluorinated vinyl film completely peeled off during a one-year outdoor exposure test, and yellowing of the glass fiber-reinforced unsaturated polyester resin layer was observed. Furthermore, for comparison, an ordinary gel-coated FRP board with a thickness of 1.0 mm obtained using a mixture composition of unsaturated polyester resin and glass fiber having the same composition as that used in Example 1 was prepared. (H) was manufactured, and this FRP board, (H), and the flat plate (A) obtained in Example 1 were subjected to an accelerated weathering test using a dual-cycle weather meter, and the irradiation time and total light The relationship with transmission retention was investigated. The results obtained are shown graphically in FIG. As is clear from Fig. 2, the flat plate (A), which is an example of the present invention, is better than the ordinary FRP plate (H),
It can be seen that the total light transmission retention rate is quite excellent. The composite reinforced plastic board and the manufacturing method thereof of the present invention are constructed as described above. It has excellent properties such as transparency, weather resistance, and especially resistance to yellowing, so it can be used in fields where weather resistance is particularly required among ordinary FRP board applications, such as solar collector coatings. It has a wide range of uses, such as agricultural covering materials, lighting areas of station buildings, and civil engineering construction materials such as the roofs of arcades and pedestrian bridges. The effect is that a reinforced plastic board can be manufactured reliably and efficiently.

[Brief explanation of the drawing]

Figure 1 shows one of the composite reinforced plastic plates of the present invention.
FIG. 2 is an enlarged cross-sectional view showing an embodiment of the present invention, and is a graph showing changes over time in the total light transmittance retention of an example of the composite reinforced plastic board of the present invention and a conventional FRP board. 1...Glass fiber reinforced unsaturated polyester resin layer, 2...Adhesive layer, 3...Polyfluorinated vinyl film layer.

Claims (1)

[Claims] 1. One or more types selected from bisphenol-based unsaturated polyester resin, vinyl ester-based resin, or oligoester acrylate resin are synthesized on the surface of the glass fiber-reinforced unsaturated polyester resin layer. A polyfluorinated vinyl film layer is provided via an adhesive layer containing a resin as a resin component, and the curable synthetic resin component in the glass fiber reinforced unsaturated polyester resin layer and the adhesive layer is hardened. , the glass fiber-reinforced unsaturated polyester resin layer and polyfluorinated vinyl film layer are each firmly and integrally bonded to the adhesive layer,
Composite reinforced plastic board characterized by being fixed. 2. The composite reinforced plastic board according to claim 1, wherein the adhesive layer contains 60% by weight or less of a general or flame-retardant type unsaturated polyester resin as a resin component. 3. An adhesive containing one or more synthetic resins selected from bisphenol-based unsaturated polyester resin, vinyl ester-based resin, or oligoester acrylate resin as a resin component is applied to one side of the polyfluorinated vinyl film. After coating and pre-curing, the obtained polyfluorinated vinyl film is added to a mixed composition of an unsaturated polyester resin and glass fiber, so that the adhesive-coated surface of the polyfluorinated vinyl film is an unsaturated polyester resin. 1. A method for producing a composite reinforced plastic board, which comprises laminating a mixed composition with glass fiber so as to be in contact with the surface thereof, and then curing by heat treatment. 4. The method for producing a composite reinforced plastic board according to claim 3, wherein the adhesive contains 60% by weight or less of a general or flame-retardant type unsaturated polyester resin as a resin component. 5 A mixed composition of unsaturated polyester resin and glass fiber is injected into the adhesive-coated surface of the polyfluorinated vinyl film, so that the adhesive-coated surface of the polyfluorinated vinyl film has a mixed composition of unsaturated polyester resin and glass fiber. A method for manufacturing a composite reinforced plastic board according to claim 3 or 4, wherein the composite reinforced plastic board is laminated so as to be in contact with the surface of an object.