JPS5833085B2 - How to use glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a resin plate reinforced with glass fibers.

Specifically, the present invention relates to a method for manufacturing a glass fiber-reinforced thermosetting resin plate whose one or both sides are covered with a specific resin layer.

Thermosetting resin plates having shapes such as corrugated or flat plates are mainly made of glass fiber reinforced unsaturated polyester resin (hereinafter simply referred to as FRP).

) resin plates are commercially available.

This resin board is used for lighting windows, lighting roofs, greenhouse walls and roofs, balcony roofs, fences, etc.

Considering this purpose of use, the performance required of the FRP resin plate is windproof, rainproof, waterproof, heat retention, lighting, etc.

Windproofing, rainproofing, moisture retention, etc. can be achieved as long as the resin plate has enough strength to maintain its shape.

In this regard, commercially available FRP resin plates are generally satisfactory.

Regarding daylighting performance, it is necessary to have a high degree of light transmittance, but although commercially available FRP resin plates show satisfactory performance in the initial stage of use, their performance deteriorates in a short period of time. It has a serious drawback.

This is because the FRP resin plate is a composite material of glass fiber and unsaturated polyester resin, and the glass fibers are arranged very far to the surface. is exposed, and the glass fiber part becomes white or has dust attached, which not only obstructs the transmission of light, but also
Furthermore, rainwater etc. can enter the interface between the glass fiber and the resin, making the interfacial adhesion between the two insufficient, causing the glass fiber to whiten, and this whitening to extend into the interior of the board along the glass fiber, significantly reducing light transmission. This is based on the fact that it can prevent

This whitening phenomenon induces a decrease in the strength of the FRP resin plate.

Therefore, attempts have recently been made to cover the surface of FRP resin plates with a thin resin layer to prevent exposure of the glass fibers.

For example, methods such as forming an unsaturated polyester resin layer on the surface or adhering a thermoplastic resin film have been proposed.

However, with the former method, it is extremely difficult to form a uniformly thin film, and several improvements are still required before it can be used industrially, and with the latter method, the thermoplastic resin film is extremely expensive. Therefore, it is not a practical method.

The present inventors have conducted intensive research to overcome the drawbacks of conventionally known resin plates and obtain a glass fiber-reinforced thermosetting resin plate with excellent lighting performance. Hydroxy prepolymers containing multiple hydroxyl groups, organic peroxides, polyfunctional isocyanate compounds,
Furthermore, by using a specific resin composition that is blended with an organic solvent that does not contain active hydrogen as necessary, it is possible to form a uniform and thin resin layer on the surface of the resin plate, and it has excellent lighting performance. The present invention was completed by discovering that resin plates can be manufactured easily and inexpensively.

That is, the present invention supplies a liquid thermosetting resin and glass fibers onto a first film that moves on a moving table, forms a glass fiber impregnated layer of the resin, and presses the glass fibers with continuous nylon fibers. Alternatively, a second film is placed on the layer without pressing, and the layer is sandwiched between the first film and the second film, and then a defoaming process is performed to defoam the layer and shade the layer. When producing a resin plate by curing the resin, with or without doing so, in advance, apply 100 parts by weight of the unsaturated polyester resin A to one or both of the surfaces of the film that will be in contact with the layer. 85 to 200 parts by weight of a hydroxy prepolymer containing multiple hydroxyl groups in one molecule, 0 to 300 parts by weight of an organic solvent C that does not contain active hydrogen, 0.3 to 5 parts by weight of organic peroxide D, and isocyanate groups. polyfunctional isocyanate in an amount such that the number of moles of is 0.5 to 1.7 times the total number of moles of hydroxyl groups and carboxyl groups contained in both unsaturated polyester resin A and hydroxy prepolymer B. It is characterized in that a resin composition containing compound E is applied and precured at a flow rate in the range of 10 to 180'C.

The first film and the second film used in the present invention are used to keep the glass fiber-impregnated layer of the liquid thermosetting resin in a constant shape until the resin is cured, and to move it in the moving direction of the moving table.

As such a napilm, for example, cellophane, vinylon, tetoron, etc. can be effectively used.

When cellophane or vinylon is used, it can be used as a protective film without peeling off from the resin plate.

When Tetoron is used, it can be used in the same way as cellophane and vinylon, but it can be peeled off after the liquid thermosetting resin is cured, and the film can be recycled.

An endless belt conveyor is effective as a moving platform.

Examples of the liquid thermosetting resin include unsaturated polyester resin, epoxy ester resin, and spiran resin, and the amount of the resin supplied onto the first film depends on the thickness of the intended resin plate. It can be produced in a wide range of quantities.

Unsaturated polyester resin is an unsaturated polyester resin prepared by subjecting an acid component containing an unsaturated dibasic acid such as maleic anhydride or maleic acid to a polycondensation reaction with an alcohol component containing a polyhydric alcohol such as ethylene glycol or propylene glycol. It is obtained by making a saturated polyester compatible with a polymerizable vinyl monomer such as styrene or acrylic acid ester, and commercially available products can be effectively used.

Epoxy ester resins are made by dissolving the reaction product of a bisphenol type epoxy resin with an unsaturated basic acid such as acrylic acid or methacrylic acid, and a polymerizable monomer such as styrene or methylmethacrylate. Commercially available products can be effectively used.

In actual use, that is, when supplying the liquid thermosetting resin onto the first film, a curing catalyst and a coloring agent for the resin or various additives such as ultraviolet absorbers and curing accelerators are added as necessary. It is added.

For example, when using an unsaturated polyester resin as a liquid thermosetting resin, a curing catalyst such as methyl ethyl ketone peroxide or benzoyl peroxide, a coloring agent, or an ultraviolet absorber or a curing agent such as cobalt octenoate as necessary. A promoter or the like is added and then supplied onto the first film.

As the glass fiber, glass fiber roving is mainly used.

In actual use, the glass fiber roving is cut to a desired specific length with a roving cutter and is sprinkled directly onto the first film to achieve a uniform distribution, or a liquid thermosetting film is supplied to the first film. Supplied by sprinkling onto the resin.

Other types of glass fiber include chopped strand mat, which is made by cutting glass fibers in advance and fixing them in a mat shape with adhesive, and glass fiber filaments that are evenly distributed in random directions and stacked and bonded with adhesive. Surf Ace: A mat made of a thin non-woven fabric can be used.

Moreover, when manufacturing a flat resin plate, glass fiber cloth, roving cloth, etc. can also be used.

Continuous nylon fibers are used as needed, but their main purpose is to hold down the glass fibers to help impregnate the fibers with liquid thermosetting resin, and for defoaming and shading processes. The purpose is to prevent glass fibers from moving during operation and causing dispersion of the fibers.

As continuous nylon fibers, roving-like filaments made by bundling filaments without twisting are most suitable, but twisted thread-like fibers can also be effectively used as long as they have an outer diameter of 0.3 mm or less.

Conventionally known methods can be used to use the continuous nylon fibers. For example, after supplying the liquid thermosetting resin and glass fibers onto the first film, continuous fibers of nylon are used at regular intervals along the moving direction of the moving table. The most effective method is to supply multiple continuous nylon fibers.

The defoaming process is a process of removing air bubbles present in the glass fiber impregnated layer of liquid thermosetting resin, and is carried out by applying pressure to the layer with two rolls through the first film and the second film. Common.

The shading step is not necessary when producing flat resin plates, but is necessary when producing corrugated plates to give the desired waveform, and generally irregularly shaped rolls are used. It is done.

Curing of the liquid thermosetting resin is carried out in the presence of a curing catalyst, if necessary in combination with a curing accelerator, at a temperature in the range of 20 to 150°C.

For example, when an unsaturated polyester resin is used as the liquid thermosetting resin, and when curing is carried out at a relatively low temperature in the range of 20 to 50°C, an organic peroxide as a curing catalyst and octenoic acid as a curing accelerator are used. When a metal soap such as cobalt is present and curing is carried out at a relatively high temperature in the range of 50 to 150°C, it is common to not use a metal soap in combination.

The resin composition used in the present invention consists of an unsaturated polyester resin A, a hydroxy prepolymer B, an organic peroxide, a polyfunctional isocyanate compound E, and an organic solvent C if necessary.

As the unsaturated polyester resin A, the same unsaturated polyester resin as the liquid thermosetting resin described above can be effectively used.

Hydroxy prepolymer B is a prepolymer containing a plurality of hydroxyl groups in one molecule, and includes, for example, a prepolymer obtained according to the following procedure.

That is, acid components mainly composed of dibasic acids represented by phthalic anhydride, tetrahydrophthalic acid, and adipic acid, and acid components represented by ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, and sorbitol in one molecule. and a polyhydric alcohol containing two or more hydroxyl groups to have a hydroxyl value in the range of 20 to 350, preferably 40 to 200, and a molecular weight of 500 to 5.000, preferably 1. ，
Prepolymers ranging from 000 to 4,000 (hereinafter referred to as
It is simply called polyester polyol.

), or one or two or more in one molecule represented by allyl alcohol, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, etc. The hydroxyl value obtained by solution polymerization, suspension polymerization, or emulsion polymerization of a monofunctional vinyl compound containing (meth)acrylate having a hydroxyl group as at least a part of its constituent components is in the range of 20 to 3501, preferably 40 to 200. and has a molecular weight of 3,000~
200,000, preferably 6,000-100,00
0 (hereinafter simply referred to as hydroxyvinyl prepolymer).

), etc. If the molecular weight of the polyester polyol is less than 500, the physical properties of the cured resin composition will be brittle, while if it exceeds 5.000, it will tend to gel during the polycondensation reaction between the acid component and the polyhydric alcohol, which is preferable. do not have.

If a hydroxyvinyl prepolymer with a hydroxyl value of less than 20 is used, the curing of the resin composition will be insufficient because there are few functional groups that can react with the polyfunctional isocyanate compound E; If a compound exceeding the hydroxyl value is used, hydroxyl groups will remain even after the reaction with the polyfunctional incyanate compound E, resulting in poor water resistance of the cured resin composition. If used, the cured product becomes too hard and expensive, which is not preferable.

If the molecular weight of the hydroxyvinyl prepolymer is less than 3,000, it will be difficult to control the molecular weight during the preparation of the prepolymer.On the other hand, if the molecular weight exceeds 200,000, the viscosity of the resin composition will become high and the desired A large amount of organic solvent is required to adjust the viscosity, which is unfavorable both economically and in terms of pollution control.

The amount of hydroxy prepolymer B used is in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of unsaturated polyester resin A.

If it is used in an amount less than 5 parts by weight, it is undesirable because the resin composition may easily cause repellency on the coating film when it is applied to the film, or it may cause curvature on the film when it is pre-cured. On the other hand, if it is used in an amount exceeding 200 parts by weight, the proportion of unsaturated polyester resin A will decrease, and the adhesive strength between the two will be reduced when the liquid thermosetting resin is cured after pre-curing the resin composition. This is not preferable because it lowers the temperature.

The organic solvent C has no active hydrogen, such as hydroxyl group, carboxyl group, or amino group, and has a boiling point of 40,200°C, preferably in the range of 60 to 150°C.

Examples of such organic solvents include aromatic compounds, halogenated aromatic compounds, aliphatic compounds, halogenated aliphatic compounds, esters, ketones, ethers, ester ketones, and vinyl compounds. Examples include toluene, xylene, methyl ethyl ketone, butyl acetate, methyl acetoacetate, styrene, methyl acrylate, trichloroethane, and benzene chloride.

Organic solvent C can be used by adding it directly to unsaturated polyester resin A, or when organic solvent C other than vinyl compounds is used, it can be used as a solvent when preparing hydroxy prepolymer B by a solution polymerization procedure. It can also be used and added as a mixture with hydroxy prepolymer B.

The amount used is in the range of 0 to 300 parts by weight, preferably 0 to 200 parts by weight, based on 100 parts by weight of the unsaturated polyester resin A.

A large amount of polymerizable vinyl monomer contained in unsaturated polyester resin A and/or hydroxy prepolymer B
If the molecular weight of hydroxy prepolymer B is small, it is not necessary to use organic solvent C, but if the molecular weight of hydroxy prepolymer B is large and organic solvent C is not used, the viscosity of the resin composition will increase and the composition will This is not preferable since it becomes difficult to coat the film.

However, when used in an amount exceeding 300 parts by weight,
The viscosity of the resin composition decreases, which is also unfavorable from the economic and pollution prevention standpoints.

The organic peroxide is used to cure the unsaturated polyester resin A, and the amount used is 0.3 to 5.0 parts by weight, preferably 5.0 parts by weight, per 100 parts by weight of the unsaturated polyester resin A. ~3.0 parts by weight.

If the amount used is less than 0.3 parts by weight, the curing of the unsaturated polyester resin A will be insufficient, and even if it is used in an amount exceeding 5.0 parts by weight, there will be no proportional effect. This is not as expected, and on the contrary, it is undesirable because the cured product only contains a large amount of decomposition residue of the organic peroxide.

The polyfunctional isocyanate compound E is an organic compound having a plurality of isocyanate groups, that is, at least two isocyanate groups in one molecule, and includes, for example, tolylene diisocyanate, prepolymers such as tolylene diisocyanate trimers, Prepolymers such as trimers of methylene diisocyanate and hexamethylene diisocyanate, xylylene diisocyanate, dimeryl diisocyanate, bis(4-incyanatocyclo\xyl)
Typical examples include methane, hydrogenated tolylene diisocyanate, and 1,5-naphthalene diisocyanate.

Furthermore, among prepolymers of a polyfunctional isocyanate compound and a polyfunctional alcohol, prepolymers in which two or more incyanato groups remain in one molecule can also be used effectively, but it is particularly desirable that the prepolymers be resistant to yellowing when exposed to ultraviolet rays. It contains less aliphatic isocyanate.

The amount of polyfunctional isocyanate compound E used is determined by the number of moles of isocyanate groups contained in compound E being the sum of the number of moles of hydroxyl groups and the number of moles of carboxyl groups contained in both unsaturated polyester resin A and hydroxy prepolymer B. quantity 0
．． The amount is 5 to 1.7 times, preferably 0.8 to 1.4 times.

If it is used in an amount where the number of moles of isocyanate groups is less than 0.5 times, the curing of the resin composition may be insufficient or a large amount of hydroxyl groups may remain in the cured product, resulting in poor water resistance of the cured product. Performance such as durability and stain resistance deteriorates, and conversely, it becomes 1.7
If more than twice the amount is used, a large amount of isocyanate groups will remain in the cured product, which will deteriorate the properties of the cured product such as water resistance and stain resistance, which is not preferable.

Various methods can be used to apply the resin composition to the film.

For example, doctor knife, roll coater, spray,
A method of applying using a brush, a flow coater, etc. can be adopted.

The coating amount is such that the thickness of the coating film after pre-curing is 0.02 to 0.5.
The amount is preferably in the range of 0.03 to 0.1.

If the coating amount is too small, that is, if the coating film thickness after preliminary curing of the resin composition is less than 0.02 mm, the coating film will be melted by the liquid thermosetting resin when it comes into contact with the resin, and the resin will not meet the intended purpose. On the other hand, if the coating film thickness exceeds 0.5 mm, the amount of the composition used will increase, which will not only be economically disadvantageous but also This is undesirable because the glass fiber content decreases, resulting in a decrease in the strength of the iron plate.

Pre-curing is carried out to cure the coating film of the resin composition on the film.
This can be easily carried out by introducing the mixture into a furnace maintained at a temperature of 180°C, preferably in the range of 40 to 160°C.

Although preliminary curing is possible even at low temperatures below 10°C,
At such low humidity, preliminary curing requires an extremely long time, which is impractical.

If the humidity exceeds 1808C, the reaction will be too intense and not only will it bring about various bad results, but the economical burden of maintaining the humidity will increase, making it impractical.

At this time, the degree of preliminary curing can be set within a wide range, but if the curing is incomplete, the resin composition and the liquid thermosetting resin will become integrated and it will not be possible to prevent the glass fibers from being exposed. The desired resin plate cannot be obtained.

On the other hand, if the liquid thermosetting resin is completely cured, the adhesion between the two will deteriorate, and cracks will occur in the cured coating of the resin composition during shaping, resulting in the resin composition not being as intended. It's something you can't get a board for.

To explain the present invention using the principle process diagram, the moving table (
A knife coke 2 is used to apply a resin composition 3 onto the first film 1 which is moving at a speed of 2 to 6 m/min on a roller (not shown).
is supplied in an amount such that the coating thickness after pre-curing is in the range of 0.02 to 0.5 mounds, and the mixture is introduced into a pre-curing furnace 4 maintained at a temperature preferably in the range of 40 to 160°C. Let it pre-cure.

A liquid thermosetting resin is applied from a storage tank 5 onto a pre-cured resin composition coating (not shown) to a desired resin plate thickness, for example 0.6 to 3. A glass fiber roving cut into a fixed size with a roving cutter 6 is quantitatively and continuously supplied in an amount of about 100 ml of resin. A second film 8 is placed on the layer 7, and the layer is sandwiched between the first film and the second film, and then air bubbles present in the layer are removed by passing through a defoaming roll 9, and the layer is formed into, for example, a corrugated shape. At the same time as the resin is cured, the pre-cured resin composition coating is completely cured by introducing it into a curing furnace 10 maintained at a temperature in the range of 10 to 150°C, with or without attaching. The resin plate 12 is pulled by a pulling device 11, the first film and the second film are peeled off, and cut into desired dimensions by a cutter (not shown) to obtain the desired resin plate 12.

The resin plate thus obtained is reinforced with glass fiber, has a thickness of approximately 0.6 to 3 mm, and has a thickness of about 0.6 to 3 mm.
The surface on the film side is covered with a layer of cured resin composition.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Note that parts in the layers mean parts by weight unless otherwise specified.

Reference Example 1 Maleic anhydride 9 was placed in a flask equipped with a stirrer, hygrometer, partial condenser, inert gas inlet tube, and heating device.
8 parts, 148 parts of phthalic anhydride, and 160 parts of propylene glycol.

An esterification reaction was carried out at a temperature of 200'C while nitrogen gas was introduced to obtain an unsaturated polyester having an acid value of 30 and a hydroxyl value of 35.

60 parts of this unsaturated polyester was dissolved in 40 parts of styrene together with 0.005 parts of hydroquinone to produce an unsaturated polyester resin (hereinafter simply referred to as resin "■").

) was obtained. Reference Example 2 In a four-eye flask equipped with a stirrer, a cooler, a thermometer, an air inlet tube, and a heating device, a bisphenol-type epoxy resin with an epoxy equivalent of 473 (manufactured by Ciba Co., Ltd., "Araldite + 607") was added.
1) Prepare 946 parts, 176 parts of methacrylic acid, 0.1 part of hydroquinone and 3.2 parts of triethylamine,
The reaction was carried out at 110°C for 5 hours while introducing air, and the acid value reached 7.
The reaction was terminated when .

Next, 748 parts of styrene monomer was added to the system containing the reaction product, and an epoxy ester resin (hereinafter simply referred to as "Kawa") was added to the system containing the reaction product.
It is called.

) was obtained.

Reference Example 3 Into a flask equipped with the same equipment as used in Reference Example 1, 13.6 parts of pentaerythritol, 127.2 parts of diethylene glycol, and 177.6 parts of phthalic anhydride were charged, and while nitrogen was introduced, the flask was heated to 230°C. An esterification reaction was carried out at high temperature to obtain a polyester polyol having an acid value of 5.1 and a hydroxyl value of 70.3.

Dissolve 50 parts of this polyester polyol in 50 parts of toluene and dissolve the polyester polyol resin (hereinafter simply referred to as resin).
It is called rlJ.

) was obtained. Reference Example 4 119 parts of methyl methacrylate, 129 parts of ethyl acrylate, 69 parts of butyl acrylate, 83 parts of 2-hydroxyethyl methacrylate, 2 parts of benzoyl peroxide, Charge 400 parts of butyl acetate and heat to 100'C.
A polymerization reaction is carried out at a temperature of 50% butyl acetate solution of an acrylic polyol having a hydroxyl value of 100 (hereinafter simply referred to as "resin-shun").

) was obtained. The molecular weight of this acrylic polyol is
Gel permeation chromatography (G, P, C
), it was 9,500.

Example 1 100 parts of resin "I", 60 parts of resin "111J", 1.0 part of benzoyl peroxide, 1-/L of 6-diSmoji
28
A resin composition was prepared.

Using a knife caulk, the resin composition was applied at a rate of 809/m2 onto the first film made of Tetron, which was being moved on a moving table.
The sample was applied in an amount of 100° C., and then introduced into a precuring oven maintained at a temperature of 100° C. and precured for 3 minutes.

The thickness of the pre-cured film was 0.067 m71. Precured resin composition coating surface (hereinafter simply referred to as gel coach surface).

) on top of the resin - 1.000 g/m2 of a resin solution containing 2 parts of benzoyl peroxide per 100 parts of Ij.
300 g/g of glass fiber roving cut into lengths of 50 crIL on top of the
A glass fiber impregnated layer of resin "I" is formed by continuously dispersing the glass fibers in a uniform amount in a proportion of
A film (on which the gel coated side had been separately formed in the same manner as in the first film) is placed, and the layer is applied to the first film.
The film is sandwiched between a second film and then passed between two rolls to substantially completely remove air bubbles in the layer.
The resin-rlJ was cured by introducing it into a curing furnace kept at a temperature of 0°C, and at the same time the gel coated surface was completely cured.The first film and second film were peeled off by pulling with a pulling device, and the size was 910 x 1820 mm. A flat glass fiber-reinforced resin plate with a thickness of 1.0 mm that was cut and gel-coated on both sides (hereinafter simply referred to as flat plate-rIJ)
I got it.

The light transmittance of the flat plate "I" was measured using an integrating sphere type reflection transmittance meter RM-I manufactured by Murakami Color Co., Ltd.

The results were a diffuse transmittance of 10%, a linear transmittance of 78%, and a total transmittance of 88%.

The weather resistance of the flat plate "l" was measured using a dual cycle weather meter model WE-8UN-DC manufactured by Toyo Rika Kogyo according to the following procedure.

That is, after irradiating the flat plate "I" for 1 hour, spray cold water from the back side for 1 hour, repeat both operations, 1.2
00 hour weather resistance test.

Then, the light transmittance is measured.

As a result of the weather resistance test, it was found that the surface condition of Plate-11J was almost unchanged from before the test.

Moreover, the light transmittance after the test was 27% in diffuse transmittance, 58% in straight line transmittance, and 85% in total transmittance.

Example 2 In Example 1, resin-In was used instead of resin-rIJ.
A flat glass fiber-reinforced resin plate (hereinafter simply referred to as a flat plate-rIJ) having a thickness of about 1.0 mm was used in the same manner, except that a glass fiber-reinforced resin plate was used.

) was obtained. The light transmittance of this flat plate-rIIJ was measured in the same manner as in Example 1.

Diffuse transmittance 11%, linear transmittance 79%, total transmittance 90%
The results were obtained.

In addition, there was almost no change in the surface condition after the weather resistance test.
Diffuse transmittance 26%, linear transmittance 55%, total transmittance 81%
Met.

Example 3 A resin composition was prepared by adding 140 parts of resin IVJ, 2.5 parts of benzoyl peroxide, and 58 parts of Dismodur N-75 to 1100 parts of resin-1-1.

Using a roll coater, the resin composition was applied onto the first film made of Tetron, which was being moved on a moving table.90! 9/m
It was applied in an amount of 2:2 and then introduced into a pre-curing oven maintained at a temperature of 110° C. and pre-curing for 2 minutes.

The thickness of the pre-cured film was 0.07 mm. Hereinafter, in the same manner as in Example 1, a flat glass fiber reinforced resin plate (hereinafter simply referred to as flat plate-Ill) with a thickness of 1.0 mm and gel coated on both sides was prepared.

) was obtained. Regarding the flat plate-rIIIJ, the light transmittance was measured in the same manner as in Example 1.

Diffuse transmittance 10%, linear transmittance 80%, total transmittance 90%
The results were obtained.

After the weather resistance test, the surface condition remained unchanged from before the weather resistance test, with a diffuse transmittance of 22%, linear transmittance of 67%, and total transmittance of 89.
%Met.

Example 4 Using a knife coater, the same resin composition as used in Example 1 was applied onto the first film made of Tetron, which was moved on a moving platform, for 80 minutes. ! / m2 and apply at a rate of 1oo
The sample was introduced into a pre-curing furnace maintained at a temperature of 0.95 C and pre-cured for 3 minutes.

The thickness of the pre-cured film was 0.061 m.

1. Apply a resin solution containing 2 parts of benzoyl peroxide to 100 parts of resin "I" on the gel coat surface. O
Continuously spray at a rate of OO97m2, and on top
30011,4.glass fiber roving cut to a length of 0 cIfL. ．． A glass fiber-impregnated layer of resin-rIJ is formed by continuously dispersing the resin-rIJ in a uniform amount, and a second film made of Tetron is placed on the layer, and the layer is mixed with the first film and the second film. The layer is sandwiched between two films, then passed between two rolls to virtually completely remove air bubbles in the layer, and then introduced into a curing oven maintained at a temperature of 100°C, and shaped using the rolls. The resin "l" is cured while being shaped into a wave shape, and at the same time the gel coated surface is completely cured.The first film and the second film are peeled off by pulling with a traction device, and 910X
Cut to size 1820mm, gel coated on one side, thickness 1. Qii corrugated glass fiber reinforced resin plate (hereinafter simply referred to as corrugated plate-rIJ).

) was obtained. A weather resistance test was conducted on the corrugated plate-rIJ.

The surface condition of the corrugated plate-rIJ was excellent with no substantial change from before the test.

Comparative Example 1 Resin-“I” is placed on the first film that moves on a moving table.
A resin solution containing 2 parts of benzoyl peroxide per 100 parts was continuously sprayed in an amount of 1.10097 m2, and a glass fiber roving cut into a length of 50 crfL was sprinkled on top of it at a rate of 30 oVm2. A glass fiber-impregnated layer of resin "1" is formed by continuously dispersing the glass fibers in a uniform amount, and a second film made of Tetron is placed on the layer, and the layer is separated from the first film and the second film. The layer is sandwiched with a film, then passed between two rolls to substantially completely remove air bubbles in the layer, and then introduced into a curing furnace maintained at a salinity of 100°C to cure the resin-rIJ. , towed by a towing device, the first
Peel off the film and the second film, 910 x 182
A flat glass fiber-reinforced resin plate cut into a size of 0 mm and having a thickness of LO mm (hereinafter simply referred to as a comparative flat plate-rIJ)
It is called.

) was obtained. The light transmittance of this comparative plate-rIJ was measured in the same manner as in Example 1.

Diffuse transmittance 14%, linear transmittance 74%, total transmittance 88%
The results were obtained.

After the weather test, the surface condition was extremely poor compared to before the test.
The glass fibers are significantly exposed, and the diffused transmittance is 52%.
The linear transmittance was 20% and the total transmittance was 72%.

[Brief explanation of the drawing]

FIG. 1 shows the principle process diagram of the present invention, with symbols 1: first film, 2: knife coater, 3: resin composition, 4
: Pre-curing furnace, 5: Liquid thermosetting resin storage tank, 6: Roping cutter, 7: Resin glass fiber impregnated layer, 8: Second
Film, 9: Defoaming roll, 10: Curing furnace, 11: Traction device, 12: Resin plate.

Claims (1)

[Claims] 1. A liquid thermosetting resin and glass fibers are supplied onto the first film that moves on a moving table, a glass fiber-impregnated layer of the resin is formed, and the glass fibers are pressed with continuous nylon fibers or pressed. Then, a second film is placed on the layer, the layer is sandwiched between the first film and the second film, and then a defoaming process is performed to defoam the layer, with or without shading the layer. When curing the resin to produce a resin plate, preliminarily apply a plurality of resins per molecule to 100 parts by weight of unsaturated polyester resin A on the surface of one or both of the films in contact with the layer. 85 to 200 parts by weight of hydroxy prepolymer containing hydroxyl groups, 300 parts by weight of organic solvent CO containing no active hydrogen, 0.3 parts by weight of organic peroxide
~5 parts by weight and the number of moles of incyanato groups is 0.5 to 1.7 times the total amount of the number of moles of hydroxyl groups and the number of moles of carboxyl groups contained in both unsaturated polyester resin A and hydroxy prepolymer B. Applying a resin composition containing an amount of polyfunctional isocyanate compound E,
A method for producing a resin plate reinforced with glass fibers, which comprises precuring at a temperature in the range of 10 to 180°C.