JPS63248831A - Production of onyx-like articles made of glass fiber-reinforced resin - Google Patents

Abstract

PURPOSE:To obtain the title articles having excellent heat resistance and water resistance as well as good appearance, decorative properties and high diversifiability in products by forming a material containing a specific polymerizable syrup, a metal oxide hydrate and glass fibers. CONSTITUTION:A polymerizable syrup giving a cured product of 1.55-1.57 refractive index at room temperature is obtained by mixing 65-45wt.% of a monomer mixture containing, as essential components, an aliphatic polyfunctional (meth)acrylate and an aromatic vinyl compound with 35-55wt.% of an aromatic vinyl polymer. Then, 100pts.wt. of (A) the polymerizable syrup are combined with (B) 200-500pts.wt. of a metal oxide hydrate, (C) 10-200pts. wt. of glass fibers and (D) a curing agent to give a pasty or solid molding material. The material is formed by curing with heat under pressure to give the subject articles.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an onyx-like article made of glass fiber reinforced resin. More specifically, it is heat-resistant and water-resistant, which is characterized by heating and pressure molding a clay-like or solid molding material at room temperature obtained by blending a metal oxide hydrate and glass fiber with a specific polymerizable syrup. This invention relates to a method for producing an onyx-like transparent appearance article made of glass fiber reinforced resin with high properties.

BACKGROUND OF THE INVENTION Flame-retardant articles prepared by pouring a mixture of a polymerizable syrup of methyl methacrylate and aluminum hydroxide into a mold and solidifying it are known as architectural decorative materials.

This item (b) is an astronomical stone-like item that scatters light beautifully, but its transparency is extremely low, and the onyx-like appearance is difficult to describe. There were problems with water resistance, such as durability deterioration.

In order to solve this problem, the present inventors have developed a method for producing onyx-like articles that are cast and cured at room temperature.
proposed that beautiful onyx molded products could be obtained by adjusting the refractive index of a solidified product of a specific polymerizable syrup to 1.51 to 1.55 at room temperature (Japanese Patent Laid-Open No. 6
0-199616).

However, when the polymerizable syrup described in JP-A-60-199616 is molded under heat and pressure, rapid shrinkage during curing may cause interfacial peeling between aluminum hydroxide and the cured resin, and There is a drawback that the thermoplastic polymer separates, precipitates, or foams during curing, resulting in the resulting cured article being opaque. Furthermore, if the cured resin is reinforced by blending glass fiber, there is also the problem that the transparency of the cured article is further impaired.

In this way, it has excellent product shape diversity and productivity, and is also water resistant as a heat/pressure molded product reinforced with glass fibers, such as a press molded product or an injection molded product made of glass fiber reinforced resin. At present, it is not possible to obtain an article with an English-Japanese A-nics appearance that is rich in quality and poor in transparency.

(Problems to be Solved by the Invention) The present inventor has arrived at the present invention as a result of intensive research to improve the current state of the conventional technology as described above. 1 Therefore, the object of the present invention is to provide aesthetic and decorative properties comparable to cast-molded products made of methyl methacrylate-based polymerizable syrup, and BMC.
Another object of the present invention is to provide a method for producing an onyx-like article made of glass fiber reinforced resin, which can produce a product that has a variety of product shapes and productivity comparable to SMC, and is highly heat resistant and water resistant.

(Means and effects for solving the problems) The present invention has the following features:
A monomer mixture containing an aliphatic polyfunctional (meth)acrylate]- and an aromatic vinyl compound as essential components (A) 65 to 45% by weight and an aromatic vinyl polymer (8) 35 to 55% by weight and the refractive index of the cured product is +1.55-1 at room temperature.
．． The syrup (I>100 hydrates of C metal oxides (
II) 200-500 heavy space and 1it glass fiber (I
II) Onyx made of glass fiber reinforced resin, which is characterized by molding and curing a clay-like or solid molding material at room temperature obtained by adding and kneading 10 to 200,000 ω parts and a hardening agent, and heating it under pressure. It relates to the manufacturing method of prepared products.

The polymerizable syrup (1) used in the present invention is a monomer mixture (A) containing an aliphatic polyfunctional <meth)acrylate-1- and an aromatic vinyl compound as essential components, and an aromatic vinyl-based It is obtained by blending a specific amount () of a small coalescence (B),
The cured product has a refractive index of 1.55 to 1.57 at room temperature. Polymerizable syrups whose cured product has a refractive index at room temperature that is outside the above range may have poor transparency when molded and cured in combination with gold WAM compound hydrates or glass fibers. becomes.

The aliphatic polyfunctional (meth)acrylates used in the present invention include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate [-, butylene glycol 1-di(meth)acrylate, and neopendel glycol]. -Glycerin tri(meth)acrylate, glycerin tri(
These include meth)acryle-1-, trimedylolbroban l-ly(meth)acrylate-1-, dipentaerythryl-1-lehex(meth)acrylate, and the like.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, and didinylbenzene.

In addition, although the above two types are essential components of the monomer mixture (A) in the present invention, a part of the monomer mixture (A) contains (meth)acrylic acid, salts thereof, and methyl (meth)acrylate. and various (meth)acrylate monomers such as isobutyl (meth)acrylate and cyclohexyl (meth)acrylate, or other monomers and oligomers such as various macro-septumers, unsaturated polyester oligomers, fumaric acid esters, and maleimides. You can also use

However, if these other monomers or oligomers are used extensively, it may be difficult to obtain a product with high filler content and excellent flame retardancy, or the product may have poor heat resistance and water resistance. be. Also, if the boiling point of other monomers used is low,
Foaming may occur during molding, resulting in poor product appearance.

Therefore, the composition of the monomer mixture (A) is such that the refractive index of the cured product of the obtained polymerizable syrup (I) at room temperature is 1.55.
It can be freely selected as long as it is within the range of ~1.57, but in the monom#i mixture (^), aliphatic polyfunctional (meta)
Preferably, the ratio is 30 to 80% by weight of acrylate and 70 to 20% by weight of aromatic vinyl compound. Further, from the viewpoint of heat resistance and transparency of the obtained article, trimethylolpropane tri(meth)acrylate is particularly preferred among aliphatic polyfunctional (meth)acrylates, and styrene is particularly preferred among aliphatic vinyl compounds.

If the amount of aliphatic polyfunctional (meth)acrylate used is less than 30% by weight in the monomer mixture, curability tends to decrease, and it is difficult to mold the product by heating and pressure, which results in excellent heat resistance with high heat distortion temperature. It becomes difficult to obtain goods that

Moreover, if the amount exceeds 80% by weight, it becomes difficult to adjust the refractive index of the cured product of the resulting polymerizable syrup at room temperature within the above range, and it becomes difficult to obtain an onyx-like appearance article with excellent transparency.

The aromatic vinyl polymer (8) used in the present invention reduces shrinkage during molding and curing to prevent cracks and improve surface smoothness of the product, and increases the transparency of the cured product to give it an onyx-like appearance. It is essential to achieve this. Polystyrene is most suitable as such an aromatic vinyl polymer (8), but styrene copolymers such as styrene-(meth)acrylic copolymer, styrene-vinyl acetate copolymer, styrene-butadiene copolymer are also suitable. Copolymers can also be used alone or in combination with polystyrene.

When obtaining the polymerizable syrup (I), the usage ratio of the monomer mixture (υ) and the aromatic vinyl polymer (B) was 6
5-45% by weight and the latter 35-55% by weight. The amount of aromatic vinyl polymer (B) used is 35w%
If the diameter of the socket is less than 1, the shrinkage during molding and curing becomes large and cracks are likely to occur in the product, and the transparency of the cured product decreases, making it impossible to obtain an onyx-like appearance product. Also, 5
If the thickness exceeds 5% by weight, the heat deformation temperature of the molded product will be extremely lower than the molding temperature, so when taking the molded product out of the mold, it will be soft and difficult to take out, making it unsuitable for recessed seats. Moreover, the resulting cured article also has poor heat resistance.

As the gold a oxide hydrate (ff) used in the present invention, aluminum hydroxide is most suitable, but other examples include magnesium hydroxide, calcium hydroxide, etc. Among the metal oxide hydrates (II), those having an average particle size within the range of 3 to 50 microns are preferred. When the particle size is smaller than this range, the viscosity of the mixture with polymerizable syrup (I) increases, and the transparency of the resulting cured article tends to decrease. If it is too large, the dispersion becomes non-uniform and the surface smoothness of the resulting cured article tends to decrease. It is desirable that the particle size distribution is as close-packed as possible.

The amount of metal oxide hydrate (II) used is in the range of 200 to 500,111 parts per 1,001 parts of polymerizable syrup (I). In amounts less than 200 parts by weight,
It is not possible to obtain a clay-like or solid molding material at room temperature that provides a flame-retardant cured article with excellent heat resistance and water resistance. Also,
If the amount exceeds 500 parts by weight, the molding material obtained by kneading will not be sufficiently impregnated into glass m1III, and will become a loose granular material with no stickiness, and even if this material is heated and pressure molded, Since there is almost no fluidity, many air bubbles remain in the molded product, making it impossible to form a high-strength cured product with a good appearance.

As the glass m1ll (I[[) in the present invention, a known glass fiber used in the art for reinforcing resin is used. However, the closer the refractive index of glass mH is to the refractive index of the cured product of polymerizable syrup (I) or the hydrate of gold amide (II), the higher the transparency of the resulting molded product. at) ff(I [I) as E-glass (refractive index 1.55 to 1,56 > or C-
Preferably, glass (1.54-1.55) is used. In addition, the length of glass fiber (III) is selected depending on the strength required for the product, but generally 1 to 611111
is preferred.

The use of glass [(I[[)] is polymerizable syrup (I)
The proportion is in the range of 10 to 200 parts by weight per 100 parts by weight, and can be increased or decreased as appropriate within the above range depending on the strength required for the product. If the amount is less than 10 parts by weight, the glass fiber reinforcing effect will be insufficient. Moreover, if the amount exceeds 200 parts by weight, a molding material with excellent fluidity during heating and pressurization cannot be obtained, and a cured article having a good onyx-like appearance cannot be obtained. Also, glass! 1t4(I[[
) may be added at the same time as the metal oxide hydrate (II) and the curing agent, but in order to prevent damage to the glass mH due to kneading, it is added after the metal oxide hydrate (II) is added. is preferable.

Examples of the curing agent used in the present invention include benzoyl peroxide, t-butyl peroxyoctoate,
There are organic peroxides commonly used in hot-press molding such as t-butyl peroxybenzoate and dicumyl peroxide, and salts of polyvalent metals and organic amines as accelerators used in combination with these organic peroxides. The curing agent is a monomer mixture (A
) is usually used in an amount corresponding to 0.5 to 360% based on the weight of .

If a silane coupling agent is used when kneading the polymerizable syrup (I), the metal oxide hydrate (It), and the glass fiber 1it (III), the product obtained by curing the molding material obtained will be This is preferred because it improves water resistance. Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyltriethoxysilane.

In addition, when kneading to obtain a molding material, various fillers other than metal oxide hydrate (I[), mold release agents such as zinc stearate, thixotropic agents, plasticizers, flame retardants and flame retardants, If necessary, a coloring agent or the like may be added within a range that does not impede the effects of the present invention.

In order to specifically carry out the present invention, for example, first, a monomer mixture (8) containing 30 to 80% by weight of aliphatic polyfunctional (meth)acrylate and 70 to 20% by weight of aromatic vinyl compound is prepared; 65 to 45 parts by weight of this mixture (A), preferably 6
0 to 501 ffi parts, aromatic vinyl polymer (B
) is added and mixed in 35 to 55 parts by weight, preferably 40 to 50 parts by weight, to make a total of 100 parts by weight of polymerizable syrup (I).
get. For 100 parts by weight of this syrup (I), 20
After adding and kneading 0 to 500 parts by weight, preferably 250 to 350 parts by weight of metal oxide hydrate (It) and a hardening agent, 10 to 200 parts by weight, preferably 15 to 50 parts by weight of glass Fiber H (Illr) is mixed to produce a clay-like or solid molding material at room temperature.

At this time, the hydrate (II) of the metal oxide is treated with a silane coupling agent in advance, or the hydrate of the metal oxide (II) used is 0.1
Water resistance of the product obtained by dissolving or dispersing a silane coupling agent equivalent to ~2.0% in the polymerizable syrup (I) and then using the metal oxide hydrate (II). can be improved. As a kneading method, for example, a low-speed mixer such as a double-arm kneader, a high-speed mixer such as a disper, a pigment dispersion machine for manufacturing paints, or a mixer roll may be used, but it is preferable to use a high-filling mixing molding material. For this purpose, a low-speed kneader with a strong mixing force is preferable.

The molding material used in the present invention is a moderately sticky, non-tacky, and easy-to-handle lump material, and can be molded and cured by various methods such as extrusion molding, press molding, injection molding, and transfer molding. A heat and pressure molding method can be used, for example, by heat and pressure molding in a mold heated to 100 to 160°C or in an extruder, a high-strength onyx with excellent surface gloss and good transparency can be produced. It can be made into a molded product.

(Effects of the invention) The molding material used in the present invention can be easily produced using a low-speed mixer such as a kneader, has excellent handling workability and storage stability, and can be manufactured for 1 to 6 months depending on the selection of the curing agent. It has a life.

According to the manufacturing method of the present invention in which this is cured under heat and pressure, it has excellent surface properties such as surface gloss and smoothness, good dimensional accuracy, little distortion, and is difficult to crack. It becomes possible to manufacture high-strength onyx-like articles of various shapes with high productivity.

In addition, the article obtained by the manufacturing method of the present invention has a high degree of flame retardancy and a high heat distortion temperature because it is highly filled with inorganic fillers, and has excellent water resistance so that it can be immersed in boiling water for up to 500%
It is a beautiful cured product that does not show any change in appearance such as whitening even after being immersed for an extended period of time, and also gives excellent results in contamination tests.

Therefore, the onyx-like products obtained by the production method of the present invention can be safely used in areas such as bathtubs and kitchen counters, which have traditionally been difficult to use due to lack of heat resistance and water resistance.

(Examples) Examples will be described in more detail below, but these do not represent the entirety of the present invention.

Example 1 50 parts by weight of polystyrene (Nisbrite T-2 beads, manufactured by Sumitomo Chemical Co., Ltd.) was added to a monomer mixture consisting of 35 parts by weight of trimethylolpropane trimethacrylate and 15 parts by weight of styrene, resulting in viscous polymerization. Got sex syrup.

The refractive index of this syrup at 1 meter is 1.5.
It was 56.

To 100 parts by weight of this syrup, 3 parts by weight of zinc stearate, a curing agent of t-4 butyl peroxyoctoate [Barbutyl 0, manufactured by NOF ■] 0.8 weight 11 NS, and a silane coupling agent (KBM-503, Shin-Etsu Chemical■!l
j) 0.5 times the weight was mixed, and the mixed solution was put into a double-arm kneader. Next, 300 parts by weight of aluminum hydroxide [Hysilite (-3201 average particle size 3.5 microns, manufactured by Showa Light Metal @ J) was added into the kneader with stirring, and finally a glass mm chop (made by E-Glass) ( A high viscosity clay-like molding material was obtained by adding 20 parts by weight (length 3ay). This molding material was a non-adhesive lump that was easy to handle.

This molding material was cut with a knife, weighed, and 2 kg was placed in a box-shaped mold (bottom surface 270 x 38 mm) set in a press molding machine.
0#11. When the product was placed in a 80m deep tank (temperature: 120°C) and press-molded using 60 tons of pressurized horn and 5 minutes of press time, it turned out to be a beautiful onyx-like molded product with a milky white translucent surface and no cracks or distortion. was obtained. The physical properties of this molded article are as shown in Table 1, and it was excellent in water resistance and flame resistance. Furthermore, the light transmittance of the 6M thick press-formed plate was 17%, and it had excellent transparency despite being highly filled with aluminum hydroxide.

Examples 2 to 4 Molding materials were prepared in the same manner as in Example 1 using the formulations shown in Table 1. All of the molding materials obtained had good handling properties.

Next, when these molding materials were press-molded under the same conditions as in Example 1, beautiful onyx-like molded products without rack or distortion were obtained, and their physical properties were as shown in Table 1. It had excellent water resistance and flame resistance. The aluminum hydroxide used in Example 3 was Hysilite 1-1-310 (average particle size 17 microns, manufactured by Showa Light Metal).

Comparative Example 1 Maleic anhydride 1110.7 mol, isophthalic MO 03 mol, neopentyl glycol 0.3 mol, propylene glycol 0.6 mol and hydrogenated bisphenol A 0.1
Unsaturated polyester 4511 obtained by condensing 5 moles
45m of styrene! An unsaturated polyester resin liquid was prepared by dissolving the unsaturated polyester resin in the ffi part and adding 5 overlapping parts of hydroquinone O and OO as stabilizers. Add polystyrene to this resin solution [Nisbright T-2 beads, manufactured by Sumitomo Chemical viJ]
10 parts by weight of zinc stearate as an internal mold release agent, 0.83 parts by weight of t-butyl peroxyoctoate as a hardening agent, and a silane coupling agent (KBM-
503, manufactured by Shin-Etsu Chemical ■] 0.5 parts by weight, aluminum hydroxide [Hisilite H-310. An average particle size of 17 microns, 210 parts by weight of Showa Light Metal R* and 15 parts by weight of glass fiber chops (3 shoes long) made of E-glass were sequentially added and kneaded in a kneader in the same manner as in Example 1. , a lumpy sticky molding material was obtained.

When 2υ of this molding material was press-molded under the same conditions as in Example 1, a beautiful white molded product was obtained.As shown in Table 1, the physical properties of the molded product were poor in transparency, water resistance, and flame resistance. It was inferior.

Comparative Example 2 To a monomer mixture consisting of 18 parts by weight of trimethylolpropane trimethacrylate and 64 mm parts of styrene, 1 part by weight of polymethyl methacrylate (Acrivet MDOO1, manufactured by Mitsubishi Rayon ■) was added to obtain a polymerizable syrup.

This syrup contains three parts of zinc stearate and one part of hardening agent.
- Mix 0.8 fflffi part of butyl peroxyoctoate (Perbutyl 01 manufactured by NOF ■) and 1 part of silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical ■), and apply this mixture to a double-arm type. It was put into a kneader. Next, aluminum hydroxide [Hisilite H-
320, average particle size 3.5 microns, Showa Light Metal Special 33
00 parts by weight were added while stirring, and finally 20 parts by weight of glass fiber chops made of E-glass (3 shoes in length) were added to obtain a high viscosity molding material. This molding material was a non-adhesive lump that was easy to handle.

This molding material was cut with a knife, weighed, and 2 kg was placed in a box-shaped mold (bottom surface 270 x 38 mm) set in a press molding machine.
0 shoes, depth 80 shoes, temperature 120℃) and press-formed with a pressure of 60 tons and a press time of 5 minutes.
Although a beautiful molded product with excellent surface gloss and no cracks or distortions was obtained, transparency was low and the desired onyx-like molded product could not be obtained.

Claims (1)

[Claims] 1. Monomer mixture containing an aliphatic polyfunctional (meth)acrylate and an aromatic vinyl compound as essential components (A) 65-45
% by weight and 35 to 55% by weight of the aromatic vinyl polymer (B), and the refractive index of the cured product is 1.55 to 1 at room temperature.
．． Polymerizable syrup (I) ranging from 57% to 100% by weight of the syrup (I) contains 200 to 500 type layer parts of metal oxide hydrate (II) and glass fiber (III).
An onyx-like article made of glass fiber reinforced resin, characterized in that a clay-like or solid molding material at room temperature obtained by adding and kneading 10 to 200 parts by weight and a hardening agent is molded and cured by heating under pressure. Manufacturing method. 2. The monomer mixture (A) is trimethylolpropane tri(
A mixture of meth)acrylate and styrene, and the former 3
The method for producing an onyx-like article according to claim 1, wherein the ratio is 0 to 80% by weight and the latter 70 to 20% by weight. 3. The method for producing an onyx-like article according to claim 1, wherein the aromatic vinyl polymer (B) is polystyrene. 4. The method for producing an onyx-like article according to claim 1, wherein the metal oxide hydrate (II) is aluminum hydroxide.