JPH06335B2 - Fiber-reinforced radical polymerization type thermosetting resin plate for surface coating and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a glass fiber reinforced thermosetting resin (hereinafter referred to as FRP) which is used by adhering to the surface of a substrate to be protected for the purpose of improving its characteristics. The present invention relates to a plate and a manufacturing method thereof.

<Prior Art> Materials such as wood and foam have drawbacks such as high water absorption and low surface hardness and strength, so objects made of these materials (hereinafter referred to as base materials). These drawbacks have been ameliorated by coating the surface of FRP with FRP. In this case, when FRP is directly laminated on the surface of the base material to cover the base material, it is difficult to eliminate the drawbacks of poor surface smoothness and poor productivity.

Therefore, at present, in order to eliminate the above-mentioned drawbacks, a method of adhering an FRP plate formed by an efficient method such as preliminarily, continuous production, or the like substantially to the surface shape of the base material to the surface of the base material. Is mainly used. However, this method is not always satisfactory. That is, in order to ensure reliable and strong adhesion between the base material and the FRP plate, polishing of the surface to be bonded of the FRP plate and degreasing with a solvent are indispensable.
The productivity is not always satisfactory, and it tends to cause new problems in the working environment due to dust and solvent. In addition, in such a system
Since it is practically impossible to color the P plate in accordance with the final needs, if coloring or patterning is required, it is carried out by Tsumotsara post-coating. Also in this case, polishing or degreasing with a solvent may be unavoidable in order to make the adhesion of the paint reliable and strong.

<Objects of the Invention> The present invention has been achieved as a result of extensive studies to solve such problems, and an object of the present invention is to reliably and firmly form a base without requiring polishing or degreasing with a solvent. An object of the present invention is to provide an FRP plate which can be adhered to a material and can be adhered to a paint, and an efficient production means of such an FRP plate.

<Disclosure of the Invention> That is, the first invention of the present application is that "a fiber-reinforced radical for surface coating is characterized in that at least one surface is in an incompletely cured state and the roughness of the surface is 50 µ or less. Polymerization type thermosetting resin plate (hereinafter abbreviated as FRP plate of the present application). "By providing the FRP plate of the present application, various problems of the prior art are solved and the object of the present invention is achieved. It is a thing.

Next, a second invention of the present application is, "A resin-impregnated glass fiber layer (hereinafter, referred to as" F ") composed of a thermosetting resin and glass fibers sandwiched between films moving in the same direction.
It is called the RP layer. In the method for continuously producing a glass fiber reinforced resin plate by curing the resin while shaping the resin if necessary, a radical polymerization type thermosetting resin is used as the thermosetting resin, and the curing step described above is used. In the case where the resin is gelled and before it is substantially cured completely,
Fiber-reinforced radical polymerization for surface coating, wherein at least one surface of the film in contact with the surface of the layer is peeled off and at least one surface is in an incompletely cured state, and the roughness of the surface is 50 μ or less. Method of manufacturing thermosetting resin plate. And the present application F by this manufacturing method.
This enabled efficient production of RP plates and improved the industrial value of the FRP plate of the present application.

In the present invention, the term "incompletely cured state" refers to a state in which tackiness is developed on the surface of the FRP plate of the present application when left standing in contact with acetone or lightly rubbed with a finger. Roughness is the irregularity of the surface that changes in a relatively short period (approximately 1 mm or less in the plane direction distance) expressed by the distance between the top and bottom of the surface. It is distinguished from "waviness", which is unevenness on the surface, which varies by about 1 to 10 mm.

At least the surface of the FRP plate of the present application that is bonded to the base material must be in an incompletely cured state. If the surface to be bonded does not meet this requirement, the object of the present invention cannot be achieved, which is not preferable. Further, in the FRP plate of the present application, the roughness of the incompletely cured surface which is bonded to the base material is 50 μm or less, preferably 40 μm or less. If the roughness exceeds this range, it becomes difficult to wet all parts of the surface with the adhesive, or the consumption of the adhesive increases,
It is not preferable because the fluctuation of the thickness of the adhesive layer becomes large and the internal strain becomes large when the adhesive is solidified and the adhesive strength is lowered. Further, the thickness of the FRP plate of the present application is not particularly limited, and various thicknesses can be manufactured according to the application, but from a general purpose of use, it is 0.3 to 10.0 mm.
It is preferable that the thickness is in the range.

The FRP board of the present invention should be produced by various methods using ordinary reinforcing glass fibers and thermosetting resins such as epoxy resin, unsaturated polyester resin, epoxy (meth) acrylate resin, unsaturated polyurethane resin, acrylic syrup and urethane resin. Is something that can be done.

Among them, the manufacturing method by the continuous molding method using the radical polymerization type thermosetting resin described above as the second invention of the present application (hereinafter, simply referred to as the second invention) is excellent in its production efficiency and the main part of the FRP plate. Is particularly preferable because it can be substantially completely cured and only an extremely thin surface layer on a predetermined surface can be efficiently controlled to an incompletely cured state.

A feature of the second invention is that a radical polymerization type thermosetting resin is used as the thermosetting resin which is a constituent component of the FRP layer, and the resin is substantially completely cured after the resin gels in the curing step. The point is that it is used in combination with the step of peeling either one of the films in contact with both sides of the FRP layer (hereinafter, simply referred to as "film peeling step"). That is, the second aspect of the present invention can exert the effect of efficiently producing the FRP plate of the present application only by using the specific resin in combination with the specific process as described above.

Even if a resin (for example, an epoxy resin or a urethane resin) other than the radical polymerization type thermosetting resin is used in combination with the "film peeling step", the action and effect of the second invention will not be exhibited.
That is, if an attempt is made to control the surface layer of the obtained FRP plate to an incompletely cured state, the entire FRP plate will be in an incompletely cured state and only a weak FRP plate will be obtained. If this is the case, the surface layer will be completely cured, and the FRP plate of the present application will no longer be suitable. Also, when the radical polymerization type thermosetting resin is used, the action and effect of the second invention cannot be exhibited unless it is used in combination with the "film peeling step". That is, if the film on one surface of the FRP layer is not used from the beginning or if the resin is peeled off before gelling, the roughness of the surface becomes large, and defoaming inside the FRP layer becomes insufficient. The FRP plate obtained for
It is unsuitable as a P plate. Conversely, when the timing of peeling the film is delayed beyond the range of the above "film peeling step", that is, when the film is peeled after the resin is substantially completely cured, from the viewpoint of surface roughness. Although there is no problem, the surface layer of the obtained FRP plate is in a completely cured state, and when the FRP plate is used, in order to ensure reliable and strong adhesion to the base material, polishing or solvent of the surface of the FRP plate is performed. Therefore, degreasing and the like are forced to be performed, and only an FRP plate which is unsuitable as the FRP plate of the present invention can be obtained. Therefore, the timing defined as "after the gelling of the resin and before the resin is substantially completely cured" in the "film peeling step" is an essential constituent requirement of the step, and the film is peeled off at this timing. As described above, the action and effect of the second invention are not exhibited, and the step of peeling the film off the specified timing does not correspond to the "film peeling step" in the present application.

The term “before substantially completely curing” in the “film peeling step” means that the FRP plate obtained by peeling the film at a certain time after the resin has gelated in the course of curing the FRP layer in a heating furnace. This means a point before the time when the surface is no longer tacky when contacted with acetone.
At such a point, an appropriate time after the resin has gelled is selected, the film is peeled off, and acetone is brought into contact with the surface of the FRP plate obtained as a result to test whether or not tackiness is exhibited. It can be easily known by repeating the simple test of slipping. In the "film peeling step" as described above, the embodiment of "peeling the film before the resin reaches the maximum heat generation after gelling" is a particularly preferable embodiment in which the characteristics of the obtained FRP plate of the present application are small. Is.

Representative examples of the radical polymerization type thermosetting resin in the present invention include unsaturated polyester resin, epoxy (meth) acrylate resin, crosslinkable acrylic syrup, unsaturated polyurethane resin, polyfunctional acrylic oligomer composition, and the like, Among them, unsaturated polyester resin and epoxy (meth) acrylate resin are particularly preferable.

The radical polymerization type thermosetting resin can be used according to the method used in the unsaturated polyester resin industry. For example, it is used together with a curing agent and optionally a curing accelerator. Further, if necessary, it can be used together with various additives and compounding materials such as a curing rate regulator, a stabilizer, an ultraviolet absorber, a colorant, a filler and an interfacial coupling agent. Regarding the types and amounts of these curing agents, curing accelerators, other additives, and compounding materials, various articles related to the unsaturated polyester resin industry have already been published (for example, "Polyester Resin" published by Nikkan Kogyo Shimbun (Eiichiro Takiyama). (Author) and Strengthening Plastics magazine (association magazine of the Strengthening Plastics Association) etc.) as is well known.

For carrying out the second invention, the FRP known in the unsaturated polyester resin industry under the newly added condition is based on the second invention "within the range satisfying the above essential constituents".
It can be carried out according to the continuous molding of the plate. For example, as the film, nylon, vinylon, saturated polyester, cellophane, etc. can be used. FR between the films
In forming the P layer, the radically polymerized thermosetting resin liquid, which is appropriately blended with the cut glass fiber, the curing agent, the curing accelerator and other additives and compounding materials, is successively placed on the moving film. And then feeding the next film, and if necessary, further repeating the operations of feeding the glass fiber and the resin liquid and further placing the film thereon to impregnate and deaerate to form an FRP layer between the films. Can be carried out according to The FRP layer may be cured at room temperature or under heating.
Among them, the method of curing under heating is preferable because of good productivity. For example, 40 to 180 ° C, preferably 60 to 1
Preference is given to working under a temperature range of 20 ° C. If necessary, the FRP plate may be shaped in the same curing step as the surface shape of the substrate.

A typical example of the second invention is as follows.

"Supply a radical-polymerization type thermosetting resin liquid containing a curing agent and other additives and compounding materials appropriately on the moving film, then sprinkle the cut glass fiber and put the film on it. Impregnation and defoaming are carried out between the rolls, and then they are introduced into a curing oven and cured, and after the resin gelates and loses its fluidity while being shaped as necessary, it is substantially completely cured. The film is peeled off from at least one side of the FRP layer at an appropriate time before filling, and further cured until the portion other than the film peeled side is substantially completely cured, and then the remaining film is peeled off or peeled off. Without doing so, the FRP plate of the present invention is manufactured by cutting into an appropriate size. ”<Effect of the Invention> The surface of the FRP plate of the present invention that is bonded to the substrate is in an incompletely cured state, and the surface roughness is 50 μ or less And because it is relatively smooth By simply adhering with an adhesive as it is, it can be firmly and firmly adhered to the substrate, and the consumption amount of the adhesive is small, which is extremely useful in industry.

Considering the fact that, as described above, the above-mentioned effects in the prior art necessitate polishing the surfaces to be bonded and cleaning with a solvent, resulting in poor productivity and causing environmental hygiene problems, the FRP plate of the present application is the first to have such effects. It can be easily understood that the excellent action and effect are exhibited.

Further, as is apparent from the above description, the operation and effect of the second invention is that the FRP plate of the present invention can be efficiently produced by an extremely simple operation, and the FRP plate of the present invention having the above characteristics can be provided at low cost.

<Examples> The present invention will be described in more detail with reference to the following examples. In the examples, "part" means "part by weight" in principle.

Each test in the examples was carried out according to the following method.

Surface roughness test A predetermined surface of the test piece was measured for a length of 10 cm with a surface roughness meter (Surfcom 2B manufactured by Tokyo Seimitsu Co., Ltd.).

Acetone test About 0.5 ml of acetone is dropped on the specified surface of the test piece and rubbed with a fingertip 10 times, and then the presence or absence of tackiness and size are checked.

Method for measuring the thickness of incompletely cured layer A 10-point mark was attached to the back surface of the predetermined surface of the test piece, the initial thickness (t ₀ ) at each point was measured with a micrometer, and then the predetermined surface was impregnated with acetone. Wipe it strongly until it is no longer tacky, then dry it and measure the thickness (t ₁ ) after removing the incompletely cured layer at each point, calculate t ₀ -t ₁ at each point, and then calculate the maximum value. , Is expressed as the thickness of the incompletely hardened layer with an average value of 8 values excluding the minimum value.

Hammer test A 10 mm thick veneer plate (30 x 30 cm) is used so that the predetermined surface of the FRP flat plate (film peeling surface, or the specially treated surface, if any) is the adhesive surface. After bonding with Toyo Polymer Co., Ltd. Rubylon K) and curing the entire surface under a load of 20 kg at 25 ° C. for 48 hours, the FRP plate side was struck with a mallet to examine whether or not peeling occurred at the bonded portion.

Example 1 Unsaturated polyester resin (Nippon Shokubai Kagaku Co., Ltd., Epo
Rack G-153AL) benzoylpa per 100 parts
-1.0 part of oxide and titanium white toner (G15
3 rolls with 100 parts of titanium and 100 parts of titanium white
0.1 part of the composition obtained by kneading with
Obtain a combined thermosetting resin liquid (hereinafter referred to as resin "I").
It was

Next, a flat plate was molded according to the following procedure in a continuous molding apparatus having the same function as the schematic diagram shown in FIG. The resin "I" is supplied at a rate of 1 kg / m ² onto a vinylon film that moves horizontally at a speed of 1 m per minute by being pulled, and glass fibers cut into a length of about 50 mm from above ( Roving) was sprayed at a rate of 300 g / m ² . Next, a vinylon film was further overlaid thereon, and then it was introduced between rolls for impregnation and defoaming. Next, both ends of the vinylon film are sandwiched between the upper and lower two films at the same time by a chuck, and both sides are pulled and moved in synchronism with the film so that the upper and lower films are kept smooth and the furnace heated to about 100 ° C is kept. FR led inside
The P layer gelled after about 5 minutes. After a further 2 minutes, knives were inserted into both ends of the film on the upper surface, cut, and peeled from the upper surface of the FRP layer. At this point, the FRP layer was a soft cured product, but by maintaining the temperature at 100 ° C for 30 minutes, a strong FR was obtained.
It became the P layer. Next, the FRP plate coming out of the curing furnace was cooled and cut to obtain an FRP plate (referred to as FRP plate (I)) having a thickness of about 1.1 mm. The film release surface of the FRP plate (I) (refers to the surface from which the film has been released before the completion of the curing step. The same applies hereafter) has a roughness of 19 μ, and the surface layer of the release surface has tackiness as a result of an acetone test. It was found to be in an incompletely cured state. The thickness of the incompletely cured layer is
It was 0.021 mm. Next, the adhesion of the FRP plate (I) was tested by a hammer test. As a result, no peeling was observed and good adhesion was exhibited.

Comparative Example 1 F of about 1.1 mm in thickness was performed in the same manner as in Example 1 except that the film on the upper surface was not peeled off in the curing furnace in Example 1.
An RP flat plate (referred to as comparative FRP plate (I)) was obtained.

The roughness of the upper surface (after film removal) of the comparative FRP plate (I) was 10 μ, and it was found by the acetone test that tackiness did not occur and the surface layer on the upper surface was completely cured. Moreover, as a result of testing the adhesiveness of the comparative FRP plate (I) by a hammer test, it was peeled at the interface between the comparative FRP plate (I) and the adhesive.

Next, the surface of the comparative FRP plate (I) was wiped with a cloth impregnated with acetone, and a hammer test was conducted in the same manner. As a result, no peeling occurred.

Example 2 The characteristics of the FRP flat plate (referred to as FRP plate (II)) obtained in the same manner as in Example 1 except that the peeling of the film on the upper surface was performed 7 minutes after the resin gelled in Example 1. Table 1 shows the results of the test.

Example 3 An FRP flat plate (hereinafter referred to as FRP plate (III)) obtained in the same manner as in Example 1 except that peeling of the film on the upper surface was carried out 13 minutes after the resin gelled.
Table 1 shows the results of checking the characteristics of the above. In this example, the FRP was about 11 minutes after the resin gelled.
The highest surface temperature of the film on the plate surface (132 ° C.) was recorded.

Comparative Example 2 FRP flat plate (Comparative FRP plate (II)) obtained in the same manner as in Example 1 except that the peeling of the film on the upper surface was performed 25 minutes after the resin gelled in Example 1. The results of testing the properties are shown in Table 1.

Comparative Example 3 Instead of performing the impregnation / defoaming of the FRP layer in Example 1 by passing between the rolls in Example 1 without using the film on the upper surface, the FRP layer was directly defoamed (circumferentially). The FRP flat plate (referred to as comparative FRP plate (III)) obtained in the same manner as in Example 1 except that it was impregnated and defoamed by pressing it with a roll having a large number of grooves along the line (1) is the result of the first test. Shown in the table.

In performing the hammer test, a comparative FRP plate (II
Other examples for adhering (I) to a plywood board (Examples 2 to 2)
About 2.5 to 3 times the amount of adhesive was required as compared with 3 and Comparative Example 2).

Examples 4 to 6 and Comparative Examples 4 to 6 In the hammer test shown in Table 1, when peeling, based on the fact that it was peeled at the interface between the FRP plate and the adhesive, FR
The following adhesion test was conducted in order to more quantitatively grasp the adhesion performance of the P plate. The results are shown in Table 2.

As is clear from Table 2, the surface-coated fiber-reinforced radical polymerization type thermosetting resin plate of the present invention had excellent adhesiveness at the interface with the substrate.

Adhesion test method Two 25 mm x 100 mm FRP plates were prepared, and the specified surfaces were adhered with an adhesive (Rubilon K) so that their edges overlap each other by 20 mm, and the width was 25 mm, the total length was 180 mm (the central part was 20 mm). I made a test piece. After adhering and curing at 25 ° C for 48 hours, both ends of the test piece are fixed with a chuck and a tensile test is performed at a pulling speed of 5 mm / min to check the maximum load (tensile strength) per unit adhesive area and the state of breakage. It was

[Brief description of drawings]

 FIG. 1 is an example of a process chart for carrying out the present invention. 1: Lower film 8: Film tenter device 2: Glass roving 9: Heating furnace 3: Glass cutter 10: Upper film cutting device 4: Glass chip 11: Upper film winding device 5: Resin "I" 12: Traction device 6: Defoaming roll 13: Resin plate (flat plate product) 7: Top film

Claims (2)

[Claims] 1. A fiber-reinforced radical polymerization type thermosetting resin plate for surface coating, characterized in that at least one surface is in an incompletely cured state and the roughness of the surface is 50 μ or less. 2. A resin-impregnated glass fiber layer (hereinafter referred to as FRP layer) consisting of a thermosetting resin and glass fibers sandwiched between films moving in the same direction, and while being shaped, the resin is cured. In the method for continuously producing a glass fiber reinforced resin plate by using a radical polymerization type thermosetting resin as the thermosetting resin, and in the curing step, the resin is substantially completely cured after gelation. A surface having at least one surface in an incompletely cured state, characterized in that at least one of the films in contact with the surface of the FRP layer is peeled off before the surface has a roughness of 50 μm or less. A method for producing a fiber-reinforced radical polymerization type thermosetting resin plate for coating.