JPS63193932A - Flat or corrugated resin plate reinforced with reinforcing fiber - Google Patents

Abstract

PURPOSE:To obtain the titled (semi)transparent flat or corrugated plate having excellent water-resistance and weather resistance, by supplying a specific polymerizable syrup and reinforcing fibers on a film using a machine for continuous forming of flat or corrugated plate, putting a film on the syrup layer to sandwich said syrup-impregnated fiber and curing the product. CONSTITUTION:A polymerizable syrup having a viscosity of 1.0-100poise at 30 deg.C is produced by mixing (A) 100pts.wt. of a liquid monomer mixture consisting of 15-55wt.% aliphatic polyfunctional (meth)acrylate, 85-45% aromatic vinyl compound and 0-40% other monomer having a boiling point of >=120 deg.C and copolymerizable with the above monomers with (B) 5-40pts.wt. of a thermoplastic polymer and (C) a curing agent. The polymerizable syrup and reinforcing fibers are supplied on to a moving film using a machine for continuous forming of flat or corrugated plate. A film moving along the moving direction of the above film is laminated on the syrup-impregnated fiber layer produced by the above process to sandwich the layer between the films. The syrup is continuously cured after or without forming the laminate to obtain the objective flat or corrugated plate suitable as a building material.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a translucent flat/corrugated plate that beautifully scatters light and can be used as a construction material with excellent water resistance and weather resistance. .

(Conventional technology) Methyl methacrylate instead of conventional technology? Flat and corrugated plates made of resin (hereinafter sometimes abbreviated as FRP) reinforced with reinforcing fibers such as remethylus fibers and organic fibers such as nylon and Tetron are well known.

(Problems to be solved by the invention) However, FRP flat and corrugated plates obtained using these known techniques have problems in productivity, water resistance, heat resistance, weather resistance, strength, and durability. The places where they could be used were limited.

For acrylic photon/corrugated plates, the curing chamber temperature during the manufacturing process is changed from 60℃ to 140℃ like unsaturated polyester resin plates.
If the temperature is raised to 70℃, methyl methacrylate, which has a low boiling point, will foam due to the heat generated by curing, leaving bubbles in the product.
It is continuously molded at the following curing temperature. Therefore, the curing time is long, and the line speed is less than 50 α/min, resulting in poor productivity and high costs. Furthermore, acrylic photon/corrugated plates have a low thermal deformation temperature of about 100° C. and are prone to thermal deformation, which limits their use in environments where heat is easily transmitted.

Flat and corrugated plates made of vinyl chloride resin had durability problems. In other words, the plasticizer is removed during use, so 1 to 2
It has the disadvantage that it loses its flexibility over time, and its impact resistance is extremely reduced, making it more likely to break.

Flat and corrugated sheets made of unsaturated polyester resin have excellent strength and durability, but the glass fibers are embossed and the appearance is poor. And when this is exposed outdoors, 2~
The disadvantage is that the glass fibers become exposed after 3 years, resulting in an opaque and dirty appearance. Although there are some improvements, the cost has increased in both cases.

The present invention aims to improve the current state of the art, and provides a flat/corrugated plate having excellent water resistance, heat resistance, weather resistance, high strength, and a beautiful transparent or translucent appearance. It is something to do.

(Means and effects for solving the problem) As a result of various studies, the present inventors have discovered that a polymerizable polymer obtained by dissolving a specific amount of a thermoplastic polymer in a mixture of specific monomers in a specific ratio. The present invention was completed by discovering that the purpose could be achieved by using silica.

That is, in the present invention, a polymerizable syrup (I) and reinforcing fibers are supplied onto a moving first film to form a fiber layer impregnated with the syrup (I), and a fiber layer impregnated with the syrup (I) is formed on the layer in the same direction as the first film. A moving second film is placed, the layer is sandwiched between the first film and the second film, and the layer is formed with or without shaping. ) Acrylate (g) 15-55]
(7%, aromatic vinyl compound (B) 85-45% by weight and other monomers C which can be copolymerized with these and have a boiling point of 120°C or higher) 0-40% by weight (However, ) and (C) component is 100% by weight.) Monomer mixture 10 Q! Polymerizable sillage (I ).

The aliphatic polyfunctional (meth)acrylates (5) used in the present invention include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. These include meth)acrylate, glycerin tri(meth)acrylate, trimethylolprono-I tri(meth)acrylate, hexa(meth)acrylate, and the like. Among them,
In terms of curing speed and heat resistance, for example, trimethylol pro-
Trifunctional (meth) represented by centrimethacrylate
Acrylate is preferred. Difunctional (meth)acrylates have a slow curing speed, and the resulting flat/corrugated sheets tend to have poor water resistance and heat resistance.

Furthermore, in the case of (meth)acrylates having four or more functionalities, the crosslinking density becomes high, and the toughness of the obtained flat/corrugated sheet tends to decrease.

The aromatic vinyl compound (B) includes, for example, styrene, α-
Examples include methylstyrene, p-methylstyrene, and divinylbenzene. Among them, styrene is preferred from the economical point of view.

The ratio of aliphatic polyfunctional (meth)acrylate (A) and aromatic vinyl compound (B) is 15 to 55% by weight, more preferably 20 to 40% by weight, and 85 to 45% by weight, It is preferably used in a proportion of 80 to 60% by weight. If the amount of aliphatic polyfunctional (meth)acrylate used is greater than the above range, the weather resistance and heat resistance of the obtained flat/corrugated sheet will be improved, but the water resistance will decrease, and the flexibility will be lost and cracking will occur. It becomes easier. On the other hand, aromatic vinyl compound (B)
If the amount used is greater than the above range, water resistance and transparency will improve, but weather resistance and heat resistance will decrease.

The monomer body temperature liquid in the present invention contains the two types of monomers (A)
and (B) is an essential component, but other monomers having a boiling point of 120°C or higher that can be copolymerized with the monomers and Φ) (C) t-monomer 40% tcs in body temperature liquid Hereinafter, it can be used preferably in a proportion of 25% by weight or less. Examples of such a monomer (C) include propyl (meth)acrylate, n-, and ls.

+, tsrt-butyl (meth)acrylate, etc.

These monomers (A), (B) and if necessary (
A monomer mixture consisting of C) alone has a viscosity that is too low to be flat or flat.
The workability during the production of corrugated sheets is poor, and the curing shrinkage is too large, causing deformation, cracking, and cracks in the product, making it impossible to use it as a polymerizable silicone for continuous molding of flat and corrugated sheets. .

The present inventors added 30 parts by weight to 100 parts by weight of the monomer mixture.
1.0 to 100 poise, preferably 3
．． If it is in the range of 0 to 30 poise, it is a polymerizable cyclo for continuous molding of flat and corrugated sheets! It has been found that a preferable product can be obtained, and that the impregnating properties into reinforcing fibers are also excellent.

That is, the polymerizable syrup (I) used in the present invention is obtained by mixing 1003 parts of the monomer mixture with 5 to 40 parts by weight of a thermoplastic/refrigerant and a curing agent, and is heated at 30°C. The measured viscosity is in the range of 1.0 to 100-Is. If the amount of the thermoplastic polymer used is small, less than 5 parts by weight, the product will easily undergo deformation, deformation, and cracks due to large shrinkage during curing. On the other hand, if 40 parts by weight is used, the impregnation into the fibers will be insufficient, and the heat resistance of the resulting flat or corrugated sheets will also be reduced.

Thermoplastic primers that can be used in the present invention include (meth)acrylate primers such as polymethyl methacrylate, (meth)acrylic-styrene copolymers, polystyrene, polyvinyl acetate, and styrene/vinyl acetate copolymers. Polymers, polybutadiene, saturated polyester, polycaprolactam, polyvinyl chloride, polyethylene, etc.

Above all, in order to improve the transparency of the obtained flat/corrugated plate and give it a beautiful appearance, it is necessary to make sure that the refractive index of the thermoplastic polymer used is the same as the refractive index of the cured product of the monomer mixture or within the range of ±O, Oa. Preferably the one in Therefore, it is desirable for the thermoplastic polymer to be used to have a composition close to that of a monomer body temperature liquid. Different copolymers are used.

Examples of the curing agent used in the present invention include penzoyl oxide, cyclohexanone tJ? -oxide, methyl ethyl ketone peroxide, bis(A-
Examples include t-butylcyclohexyl oxydicarbonate and t-butylperoxyoctoate, which are used alone or together with organic amines or polyvalent metal salts as accelerators. The amount of curing agent added is usually 0.3 to 3.0% based on the weight of the monomer mixture.

When preparing polymerizable syrup (I), the obtained plain and
In order to improve the heat resistance and flame resistance of the corrugated sheet, an inorganic filler may be mixed and dispersed. Examples of such inorganic fillers include calcium carbonate, Merck, clay, silica, alumina, quartz, calcium silicate, and hydrates of various metal oxides such as aluminum hydroxide and magnesium hydroxide.

Among these, aluminum hydroxide is preferred since it can achieve a higher degree of flame retardancy.

Furthermore, various additives and modifiers can be mixed and used in the polymerizable syrup (I). For example, silane or titanate coupling agents are used to improve interfacial adhesion between resin and reinforcing fibers, especially glass fibers, internal mold release agents and colorants are used to improve mold release properties from the film, and weather resistant Ultraviolet absorbers are used to improve properties and protect products from ultraviolet rays.

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

The FRP flat/corrugated plate of the present invention is produced using the above-mentioned polymerizable silica (I) and reinforcing fibers using a conventionally known continuous flat/corrugated plate forming machine. Specifically, for example, polymerizable syrup (I) is supplied onto the moving first film via a coating roll or a knife coater, and reinforcing fibers are also supplied onto the first film by scattering or the like. Then,
A second film moving in the same direction as the first film is placed on the polymerizable syrup (I)-impregnated fiber layer formed on the first film, and the layer is sandwiched between the two films to remove the core layer as necessary. The polymerizable sillage (I) is continuously cured while being shaped into a shape such as a shiba deafness. Curing is generally carried out by introducing the fiber layer impregnated with polymerizable syrup (I) into a curing chamber.

The curing chamber is divided, for example, so that the atmospheric temperature changes stepwise from the entrance to the exit, and the temperature is 60°C from the entrance to the center.
The temperature is set to gradually rise from 120°C to 120°C, and a cooling section is provided near the exit.

The flat and corrugated sheets of the present invention have a length of 2 to 3 m, which is the same as the flat and corrugated sheets manufactured using conventional unsaturated polyester resin.
It can be manufactured with good productivity at a line speed of /min. In addition, flat and translucent surfaces with a beautiful transparent or translucent appearance
Corrugated sheets are readily provided in accordance with the present invention.

(Effects of the invention) It has excellent water resistance that does not lose its luster, does not reduce its transparency due to whitening, and does not cause surface cracks even when immersed for more than an hour, and has a beautiful semi-transparent appearance. can be maintained for a long period of time. Further, the flat/corrugated plate of the present invention has a high thermal deformation temperature and is excellent in weather resistance.

(Examples) Examples will be described in more detail below, but these do not represent the entirety of the present invention. In addition, parts in the examples represent parts by weight unless otherwise specified.

Example 1 A methyl methacrylate-styrene copolymer (as a thermoplastic polymer) was added to a monomer mixture consisting of 30 parts of trimethylolpropane trimethacrylate and 70 parts of styrene.
Product name MASφ10. Daicel Chemical Co., Ltd. fi) 20 parts, silane coupling agent [KBM-503, Shin-Etsu Chemical Co., Ltd.
[Manufactured by Ciba Geigy] 0.5 part, ultraviolet absorber [Tinupin 3201 manufactured by Ciba Geigy] 0.1 part, curing agent t-butyl peroxyoctoate [Tsuku] was added, mixed and dissolved to obtain polymerizable syrup (I). .

The viscosity of the obtained polymerizable syrup (I) was 20 poise at 30°C.

The obtained next polymerizable syrup (I) is transferred to a continuous flat/corrugated plate production machine (
It was fed through a knife coater onto a moving first film (made of polyester) at a line speed of 2.5 m (7 min), while glass fibers were sprinkled onto the first film at a glass content of 22% by weight. .

Impregnation of polymerizable silica (I) into glass fibers and curing were performed continuously between the second film placed on the first film and the first film to form a corrugated sheet with a thickness of 0.8 m. Manufactured.

The obtained corrugated sheet was completely cured and beautiful, transparent to milky white and translucent, and as shown in Table 1, had high strength and excellent water resistance and weather resistance.

Examples Ta.

A corrugated sheet was produced in the same manner as in Example 1 using the obtained polymerizable syrup (I) and glass fiber.

The obtained corrugated sheet was beautiful and transparent, and as shown in Table 1, had high strength and excellent water resistance and weather resistance.

Comparative Example 1 Commercially available FRP corrugated sheet for building materials (made of unsaturated polyester resin)
As a result of measuring the performance, the results were as shown in Table 1, which had both advantages and disadvantages, and was not excellent overall.

Claims (1)

[Claims] 1. Polymerizable syrup (I) on the moving first film
and supplying reinforcing fibers to form the syrup (I)-impregnated fiber layer, and placing a second film moving in the same direction as the first film on the layer to separate the layer from the first film and the second film. A flat or corrugated resin sheet reinforced with reinforcing fibers obtained by sandwiching the syrup (I) with or without shaping the layers and curing the syrup (I) continuously. (Note) 15 to 55% by weight of aliphatic polyfunctional (meth)acrylate (A), 85 to 45% by weight of aromatic vinyl compound (B), and other monomers that can be copolymerized with these and have a boiling point of 120°C or higher. body (C) 0 to 40% by weight (however, (A), (B)
The total amount of component (C) is 100% by weight. ) is obtained by mixing 5 to 40 parts by weight of a thermoplastic polymer and a curing agent to 100 parts by weight of a monomer mixture consisting of Some polymerizable syrups (I). 2. Claim 1, wherein the aliphatic polyfunctional (meth)acrylate (A) is trimethylolpropane trimethacrylate and the aromatic vinyl compound (B) is styrene.
Flat/corrugated plates listed in section. 3. The flat/corrugated plate according to claim 1, wherein the thermoplastic polymer has a refractive index within a range of ±0.03 of the refractive index of the cured monomer mixture.