JPH075754B2 - Resin flat / corrugated plate reinforced with reinforcing fibers - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a semitransparent, beautifully light-scattering flat / corrugated plate that can be used as a building material having excellent water resistance and weather resistance.

(Prior art) Conventionally, a reinforcing fiber such as glass fiber or organic fiber such as nylon / tetron obtained by using syrup in which polymethylmethacrylate is dissolved in methylmethacrylate, vinyl chloride resin, or unsaturated polyester resin. Flat made of reinforced resin (hereinafter sometimes abbreviated as FRP)
Corrugated plates are known.

(Problems to be solved by the invention) However, the flat and corrugated sheet made of FRP obtained by these known techniques has problems in productivity, water resistance, heat resistance, weather resistance, strength, and durability, Each place was limited in use.

With acrylic flat and corrugated sheets, if the temperature of the curing chamber is raised from 60 ° C to 140 ° C like an unsaturated polyester resin plate in the manufacturing process, low boiling point methyl methacrylate foams due to the heat of curing and bubbles form in the product. Since it remains, it is continuously molded at a curing temperature of 70 ° C or less. Therefore, the curing time is long, the line speed is 50 cm / min or less, and the productivity is poor and the cost is high. Further, the acrylic flat / corrugated sheet has a drawback that the heat deformation temperature is low at about 100 ° C. and is easily thermally deformed, and thus there is a limitation in use in an environment where heat is easily transmitted. Furthermore, it was difficult to make it flame-retardant, and there was a problem in using it in factories and public facilities.

Flatness and corrugated sheet of vinyl chloride resin had a problem in durability. In other words, the plasticizer gradually escapes during use, so 1-2
The flexibility was lost over the years, and there was a drawback in that the impact resistance was extremely reduced and cracked easily.

Unsaturated polyester resin flat and corrugated sheets are excellent in strength and durability, but are inferior in aesthetic appearance due to the protrusion of glass fibers. And when this is exposed outdoors, 2
There is a defect that the glass fiber is exposed and becomes opaque and dirty in 3 years. To prevent this, a gel coat is applied to the surface, or a film with good water resistance and weather resistance such as vinylidene tetrafluoride film is used. I have pasted it, but both have increased costs.

The present invention is intended to improve the present situation, and is a semitransparent beautiful light-scattering flat light that has excellent water resistance, heat resistance, and weather resistance and can easily be flame retarded.・ Provides corrugated board.

(Means and Actions for Solving Problems) As a result of various studies, the present inventors have obtained a curable liquid obtained by combining a specific monomer in a specific ratio with a specific amount of an inorganic filler. The inventors have found that the object can be achieved by using, and have completed the present invention.

That is, in the present invention, the following curable liquid (I) and reinforcing fibers are supplied onto the moving first film to form the curable liquid (I) -impregnated fiber layer, and the first film and the first film are formed on the layer. A second film that moves in the same direction is placed, and the layer is sandwiched between the first film and the second film, and the curable liquid (I) is continuously cured with or without shaping the layer. The present invention relates to a resin-made flat / corrugated plate reinforced with a reinforcing fiber obtained as described above.

(Note) Aliphatic polyfunctional (meth) acrylate (A) 15 to 55% by weight, aromatic vinyl compound (B) 85 to 45% by weight, and another unit amount having a boiling point of 120 ° C. or more copolymerizable with these Inorganic filler to 100 parts by weight of a monomer mixture consisting of 0 to 40% by weight of the body (C) (however, the total of the components (A), (B) and (C) is 100% by weight). A curable liquid (I) obtained by mixing 250 to 400 parts by weight and a curing agent, and having a viscosity measured at 30 ° C. in the range of 1.0 to 100 poise.

The aliphatic polyfunctional (meth) acrylate (A) used in the present invention means ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth). ) Acrylate, glycerington (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. Above all,
From the viewpoint of curing speed and heat resistance, for example, a trifunctional (meth) acrylate represented by trimethylolpropane trimethacrylate is desirable. With a bifunctional (meth) acrylate, the curing rate is slow, and the resulting flat or corrugated sheet tends to have poor water resistance and heat resistance. Also, tetra-functional or higher (meta)
In the case of acrylate, the crosslink density becomes high, and the toughness of the obtained flat or corrugated sheet tends to decrease.

Examples of the aromatic vinyl compound (B) include styrene and α-
Methylstyrene, p-methylstyrene, divinylbenzene, etc. are available. Among them, styrene is preferable from the economical point of view.

The proportion of the aliphatic polyfunctional (meth) acrylate (A) and the aromatic vinyl compound (B) is 15 to 55% by weight in the former, more preferably 20 to 40% by weight, and 85 to 45% by weight in the latter. Is used in a proportion of 80 to 60% by weight. When the amount of the aliphatic polyfunctional (meth) acrylate (A) used is more than the above range, the weatherability and heat resistance of the resulting flat or corrugated sheet are improved, but the water resistance is lowered and the flexibility is lost. It becomes easy to crack. On the other hand, when the amount of the aromatic vinyl compound (B) used exceeds the above range, the water resistance and the transparency are improved, but the weather resistance and heat resistance are deteriorated.

The monomer mixture in the present invention is the above-mentioned two kinds of monomers (A).
And (B) are essential components, the monomer (A)
The other monomer (C) having a boiling point of 120 ° C. or higher which is copolymerizable with (B) and (B) can be used in a ratio of 40% by weight or less, more preferably 25% by weight or less in the monomer mixture. Examples of such a monomer (C) include propyl (meth)
There are acrylate, n-, iso-, tert-butyl (meth) acrylate and the like.

These monomers (A), (B) and optionally (C)
With a monomer mixture consisting of only, the viscosity is too low and the workability during flat and corrugated sheet production is poor, and the curing shrinkage is too large and the product is deformed, warped and cracked, resulting in flat and corrugated sheet. It cannot be used as a curable liquid for continuous molding.

The inventors of the present invention, by mixing and dispersing 250 to 400 parts by weight of an inorganic filler with respect to 100% by weight of the monomer mixture, the viscosity of the curable liquid after dispersion is measured at 30 ° C. to be 1.0 to 100%. It has been found that when the poise, more preferably in the range of 3.0 to 30 poises, a preferable curable liquid for continuous molding of flat and corrugated sheets is obtained and the reinforcing fiber is also excellent in impregnating property. .

That is, the curable liquid (I) used in the present invention is the inorganic filler 250 to 400 with respect to 100 parts by weight of the monomer mixed liquid.
It is obtained by mixing parts by weight and a curing agent, and the viscosity measured at 30 ° C. is in the range of 1.0 to 100 poise. When the amount of the inorganic filler used is a small amount less than 250 parts by weight,
The shrinkage at the time of curing becomes large and the product is apt to be deformed, warped or cracked, and the resulting flat or corrugated sheet has insufficient heat resistance. On the other hand, when the amount is more than 400 parts by weight, it is difficult to set the viscosity of the resulting curable liquid to 100 poises or less, and the impregnation property into the reinforcing fiber becomes insufficient.

As the inorganic filler that can be used in the present invention, calcium carbonate, talc, clay, silica, alumina, quartz, calcium silicate and hydrates of various metal oxides commonly used in the art can be used. . Among them, the cured product is semitransparent and has a beautiful appearance that scatters light beautifully, and it can be dispersed in a large amount as much as possible in order to reduce curing shrinkage, and is stable in the dispersion liquid without settling for a long time. Aluminum hydroxide having an average particle size of is preferred. Further, aluminum hydroxide is also preferable for making the flat / corrugated plate flame-retardant.

Examples of the curing agent used in the present invention include benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyoctoate and the like. Or
Used as an accelerator together with organic amines and salts of polyvalent metals. The addition amount of the curing agent is usually 0.3 to 3.0% based on the weight of the monomer mixture.

When preparing the curable liquid (I), if necessary, a thermoplastic polymer for shrinkage reduction may be dissolved in a monomer mixture and used. When such a thermoplastic polymer is used, the viscosity of the curable liquid (I) increases with an increase in the amount used, so that the viscosity range is suitable for continuous molding of flat and corrugated sheets. Need to be prepared. Examples of these thermoplastic polymers include (meth) acrylate-based polymers such as polymethylmethacrylate, (meth) acrylic-styrene-based copolymers, polystyrene, polyvinyl acetate, styrene-vinyl acetate copolymers, polybutadiene, and saturated polyesters. , Polycaprolactam, polyvinyl chloride, polyethylene, etc.

Further, various additives and modifiers can be mixed and used in the curable liquid (I). For example, surfactants and wetting agents for improving the dispersion of the inorganic filler, various coupling agents for improving the interfacial adhesion between the inorganic filler and the reinforcing fiber, particularly the glass fiber and the resin, and the weather resistance are used. An ultraviolet absorber is used for the purpose of improving the heat treatment and protecting the product from ultraviolet rays.

In order to specifically obtain the curable liquid (I) in the present invention, for example, aliphatic polyfunctional (meth) acrylate (A) 15 to 55% by weight, preferably 20 to 40% by weight, aromatic vinyl compound (B) A monomer mixture containing 85 to 45% by weight, preferably 80 to 60% by weight, and 0 to 40% by weight, preferably 0 to 25% by weight of another monomer (C) having a boiling point of 120 ° C. or higher is prepared. Then, 250 to 400 parts by weight of the inorganic filler is mixed and dispersed with a high-speed stirrer with respect to 100 parts by weight of this mixed liquid. On this occasion,
By adding and using various additives and modifiers such as the above-mentioned curing agent and a thermoplastic polymer, if necessary, the viscosity of the mixing trace is measured at 30 ° C to 1.0 to 100 poise, more preferably 3.0 to 30 poise. And the curable liquid (I). In addition,
In order to achieve this viscosity range, dispersion with a high speed stirrer is preferred.

As the reinforcing fibers, glass fibers are most commonly used, but carbon fibers and organic fibers such as polyamide / nylon / polyester can also be used.

The FRP flat / corrugated plate of the present invention is the curable liquid (I) described above.
And a reinforcing fiber, and is manufactured by a conventionally known flat / corrugated plate continuous molding machine. Specifically, for example, the curable liquid (I) is supplied onto the moving first film via a coating roll or a knife coater, and the reinforcing fiber is also supplied onto the first film by spraying or the like. Then, a second film that moves in the same direction as the first film is placed on the curable liquid (I) -impregnated fiber layer formed on the first film, and the layer is sandwiched between the two films, and the layer is formed if necessary. The curable liquid (I) is continuously cured while being formed into a corrugated shape or the like. Curing is generally performed by introducing the curable liquid (I) -impregnated fiber layer into the curing chamber.

The curing chamber is divided, for example, so that the ambient temperature changes stepwise from the inlet to the outlet, and 60 ° C from the inlet to the center.
The temperature is set to gradually rise from 120 ° C to 120 ° C, and a cooling unit is provided near the outlet.

The flat / corrugated plate of the present invention is the same as the flat / corrugated plate manufactured by the conventional unsaturated polyester resin in this manner, and is 2 to 3 m / m.
It can be manufactured with high productivity at a minute line speed. Further, the present invention easily provides a flat / corrugated plate that is translucent and has a beautiful appearance that scatters light beautifully.

(Effects of the Invention) The FRP flat / corrugated plate of the present invention has a water resistance that does not lose gloss, does not reduce transparency due to whitening, and does not cause surface cracks even when immersed in boiling water for 200 hours or more. It is excellent, and it is semitransparent and can maintain a beautiful appearance that scatters light beautifully for a long period of time. Further, the flat / corrugated plate of the present invention has a high thermal deformation temperature, excellent weather resistance, and is easily flame-retardant simply by selecting an inorganic filler.

(Examples) Hereinafter, Examples will be described in more detail, but these are not representative of all of the present invention. The parts in the examples represent parts by weight unless otherwise specified.

Example 1 0.5 part of a silane coupling agent [KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.], an ultraviolet absorber [Tinuvin 320, manufactured by Ciba Geigy Co., Ltd.] in a monomer mixture liquid consisting of 30 parts of trimethylolpropane trimethacrylate and 70 parts of styrene. Manufactured] 0.1 part, t-butyl peroxyoctoate [perbutyl 0, a curing agent,
0.5 parts of Nippon Oil & Fats Co., Ltd. and 0.1 parts of a promoter [Promoter A, manufactured by Nippon Shokubai Chemical Co., Ltd.] were added and mixed. Next, 300 parts of aluminum hydroxide [Hidilite H-320, average particle size 3.5 microns, manufactured by Showa Light Metal Co., Ltd.] was added to this mixed liquid while stirring with a high speed disper stirrer, and mixed and dispersed to cure. Liquid (I) was obtained. The viscosity of the resulting curable liquid (I) was 6 poise at 30 ° C.

The resulting curable liquid (I) was supplied onto a moving first film (made of polyester) of a flat / corrugated plate continuous production machine (line speed 2.5 m / min) through a knife coater, while glass fibers were made into glass. The content of 22% by weight was applied onto the first film. Impregnation and curing of the curable liquid (I) into the glass fiber and the second film placed on the first film and the first film
The corrugated plate having a plate thickness of 0.8 mm was manufactured by continuously performing the process with the film.

The obtained corrugated sheet was completely hardened and had a beautiful milky white translucency. As shown in Table 1, high strength and water resistance,
It was excellent in heat resistance, flame resistance, and weather resistance.

Examples 2 to 3 The same operation as in Example 1 was repeated to prepare a curable liquid (I) having a composition as shown in Table 1.

A corrugated plate was produced in the same manner as in Example 1 using each of the obtained curable liquids (I) and glass fibers.

The obtained corrugated sheet was a translucent and beautiful one, and had high strength and excellent water resistance, heat resistance / flame resistance, and weather resistance as shown in Table 1.

Comparative Example 1 As a result of measuring the performance of a commercially available building material FRP corrugated sheet (made of unsaturated polyester resin), the results are as shown in Table 1, and there are advantages and disadvantages, and they are not comprehensively excellent.

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Claims (3)

[Claims] 1. A curable liquid (I) and a reinforcing fiber described below are supplied onto a moving first film to form a curable liquid (I) -impregnated fiber layer, and the same layer as the first film is formed on the layer. A second film which moves in the direction
A resin-made flat / corrugated plate reinforced with reinforcing fibers obtained by sandwiching the film with a film and continuously curing the curable liquid (I) with or without shaping the layer. (Note) Aliphatic polyfunctional (meth) acrylate (A) 15 to 55% by weight, aromatic vinyl compound (B) 85 to 45% by weight, and another unit amount having a boiling point of 120 ° C. or more copolymerizable with these Inorganic filler to 100 parts by weight of a monomer mixture consisting of 0 to 40% by weight of the body (C) (however, the total of the components (A), (B) and (C) is 100% by weight). A curable liquid (I) obtained by mixing 250 to 400 parts by weight and a curing agent, and having a viscosity measured at 30 ° C. in the range of 1.0 to 100 poise. 2. An aliphatic polyfunctional (meth) acrylate (A)
Is trimethylolpropane trimethacrylate,
The flat / corrugated plate according to claim 1, wherein the aromatic vinyl compound (B) is styrene. 3. The inorganic filler is aluminum hydroxide having an average particle size of 5 microns or less.
Flat and corrugated sheet described in paragraph.