JPS6345160A - Manufacture of natural stone-like product - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention provides a method for mass-producing various natural stone products, particularly a method for mass-producing natural stone-like products that are highly heat resistant, water resistant, and highly decorative. It is related to.

(Prior art) Products in which an inorganic filler is mixed into a methacrylic acid ester resin are well known, and inorganic fillers are added to a silica or plastic made by prepolymerizing 10 to 30% of a methacrylic acid ester monomer. It is manufactured by a method in which a kneaded slurry is injected into a mold and hardened, or by a method in which an inorganic filler is further filled to a high level and then extruded. However, these had drawbacks such as requiring a long time to produce, limiting the shape of the product, and lacking heat resistance.

On the other hand, unsaturated polyester resin is kneaded with curing agents, fillers, reinforcing materials, thickeners, etc. to make clay-like pulp molding compounds (BMC) and L*.
A molding material called sheet molding compound (SMC) is also known, and BMC-? is a molding compound containing a thermoplastic polymer for the purpose of lowering the shrinkage rate of this molding compound.
SMC is also widely used. However, since these use polyvalent metal oxides, hydroxides, or alkoxide compounds as thickeners, they are affected by moisture and have large variations in quality, and are also prone to phase separation. It wasn't something.

(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.

Therefore, the object of the present invention is to have a variety of product shapes and mass productivity comparable to B MC + S MC without losing the beauty and decorative properties of the casting method using methacrylic acid ester resin sila, f. Furthermore, it is an object of the present invention to provide a method for producing a natural stone preparation product that can produce a product that is highly heat resistant and water resistant.

(Means and effects for solving the problems) The present invention has the following features:
Monomer (A) containing polyfunctional (meth)acrylate as an essential component, methacrylic resin powder derived from a monomer containing methacrylic acid esters as an essential component, the monomer (A),
Obtained by kneading and aging the curing agent (C), inorganic filler (B), and if necessary, the 7'6 ring agent, coloring agent, and reinforcing material in 4) at room temperature or under heating below the curing temperature. This relates to a method for producing natural stone preparations characterized by molding and hardening a clay-like or solid molding material at room temperature by heating it under pressure.・Contains polyfunctional (meth)acrylate used in the present invention as an essential component. Containing monomer (4)
contains polyfunctional (meth)acrylate as an essential component to form a crosslinked structure during molding and curing, and optionally contains other monomers that can be copolymerized with polyfunctional (meth)acrylate. It is.

Examples of the polyfunctional (meth)acrylate constituting the monomer (4) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,
Neobentyl glycol di(meth)acrylate, trimethylolpronotri(meth)acrylate, interaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. can be used, and as the monomer (4) Other monomers that can be used as necessary are effective monomers that give relatively hard polymers, and can be appropriately selected and used depending on the resin composition of the methacrylic resin powder (0). For example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, Schifta hexyl methacrylate, benzyl methacrylate, styrene, 0゜m, p-methylstyrene■
- Aromatic vinyl compounds such as α-methylstyrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate.

Examples include (meth)acrylonitrile.

The amount of polyfunctional (meth)acrylate in the monomer ratio is 20%, considering the performance such as heat resistance of the resulting natural stone preparation.
It is preferable that the amount is more than % by weight.

If the amount of polyfunctional (meth)acrylate is small (less than 20% by weight), depending on the combination with other components constituting the natural stone skin product, it will not harden to form a sufficient cross structure, resulting in poor heat resistance and water resistance. In some cases, only inferior products can be obtained.

The methacrylic resin powder 0) used in the present invention includes methyl methacrylate, ethyl methacrylate, 1so-propyl methacrylate, n-butyl methacrylate), 1so
- alkyl methacrylates such as butyl methacrylate, 2-ethylhexyl methacrylate; cycloalkyl methacrylates such as cyclohexyl methacrylate;
A monomer consisting of one or more methacrylic esters selected from aralkyl methacrylates such as benzyl methacrylate as an essential component, and optionally containing other monomers copolymerizable with dimethacrylic esters. The polymer can be obtained by suspension polymerization or emulsion polymerization without the use of external surfactants, and the polymer can be separated out by methods such as sedimentation, or by pulverizing the polymerized polymer (by bulk polymerization). It is a granular material having a thermoplastic or partially crosslinked structure. The particle size may range from 2 to 31 μm depending on the purpose, but it is usually preferred to have a particle size of 100 μm or less.

The average molecular weight of the polymer constituting the resin powder (B) is preferably 50,000 or more, and particularly 100,000 or more exhibits preferable properties in obtaining a molding material with excellent workability.

Other monomers copolymerizable with methacrylic esters that can be used to obtain methacrylic resin powder CB) include alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. or cycloalkyl acrylates, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or glycidyl electromethyl group, and n is 2 to 10. ), R' is an alkyl group, and n is 2 to 10. ), glycol mono(meth)acrylates such as neopentyl glycol mono(meth)acrylate, ethylene glycol di(meth)acrylate, 7'l=1 pyrene glycol di(meth)acrylate, etc. ) acrylate, neopentyl glycol/7(meth)acrylate, trimethylol pronobase, polyfunctional (meth)acrylates such as tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, styrene・o, nt, p-methylstyrene ・α
- Aromatic vinyl compounds such as methylstyrene, fluorine-containing sublayer saturated compounds such as trifluoroethyl (meth)acrylate, maleimide compounds such as phenylmaleimide, and one or more monomers selected from these. Quantity can be used.

The amount of methacrylic resin powder used is 100% monomer
! Ratio of 50 to 3001 parts per part If this ratio is exceeded, it becomes difficult to obtain a molding material that is clay-like or solid at room temperature in the kneading/aging chamber and has excellent workability during molding and curing.

The curing agent (C) in the present invention is an azobis compound or an organic peroxide, which is a radical polymerization initiator for monomer particles, such as azobisisobutyronitrile, benzoyl peroxide, t-tester Δ-oxide, or cumene hydroxyperoxide. It is possible to use one or more of oxide, t-butyl hydroperoxide, dicumyl peroxide, etc., dissolved in the monomer. The amount of curing agent (C) used is preferably 0.5 to 2 parts by weight per 100 parts by weight of monomer (4).

There are various inorganic fillers (b) such as calcium carbonate, kaolin, clay, alumina, silica, and magnesium oxide, but hydrated aluminum and magnesium hydroxide provide flame retardance to the product and are aesthetically pleasing. This is preferable. The particle size is preferably 100 μm or less, but especially when glass fiber or the like is used as a reinforcing material, the average particle size is preferably 5 μm or less in order to achieve high filling. Inorganic filler (
The amount used for 9) is 100 monomers! 100 per part
A proportion of ~500 parts by weight is preferred.

As the coupling agent, a mild coupling agent is used, and silane-based ones are particularly preferred.As for the coloring agent, organic and inorganic pigments are used, but metal oxide-based pigments are preferred. As the reinforcing material, organic fibers such as glass fiber, carbon fiber, and aramid fiber can be used.

In the present invention, the monomer prisoner, methacrylic resin powder (
B), the amount necessary for the hardening agent (Q, of the inorganic filler),
A near aIJ agent, a coloring agent, and a reinforcing material are blended and kneaded and aged at room temperature or under heating below the curing temperature. Kneading/
Aging must be carried out until the above-mentioned components become clay-like or solid at room temperature, but in order to sufficiently knead and disperse the inorganic filler (b), methacrylic resin powder (
It is preferable to disperse the inorganic filler prior to kneading B). This kneading and maturing is carried out using various kneading machines,
For example, it can be carried out all at once using a co-kneader, Σ-blade kneader, extruder, etc. Also, after kneading is performed in the kneader, the obtained high viscosity slurry or wet powdered autumn material is placed in a ripening room at room temperature. Alternatively, the aging may be completed by maintaining the temperature at a temperature lower than the curing temperature.

A typical method of implementing the invention will now be described. First, 100 parts by weight of monomer (4) is melted with 0.5 to 2 parts of curing agent (C), then 100 to 500 parts by weight of inorganic filler (B) is kneaded and dispersed, and finally 50 parts by weight of When methacrylic resin powder CB) with a weight of ~300% is added and kneaded, it becomes a highly viscous slurry or wet powder at room temperature. A clay-like or solid molding material is obtained.

The molding material obtained in this way does not itch, can be cut with a knife, etc., is easy to measure, and can be heated to a curing temperature while being given a shape by methods such as compression, transfer, injection, or extrusion. By proceeding with the curing process, you can obtain a natural stone-like molded product. Pressure during molding is 10-1
00 kg/ay! .

The temperature is about 80 to 160℃ and the molding time is less than several tens of minutes 4Ω
Good for a short time. Therefore, even one resin powder having a relatively high molecular weight can be molded without being decomposed, which is useful for improving various physical properties of products.

Specific examples will be explained in more detail below, but these do not cover all aspects of the present invention.

Example 1 Ethylene glycol dimethacrylate 5ooy.

trimethylolpropane trimethacrylate 500S,
An average particle size of 3 was added to the mixture of dicumyl peroxide 109 and γ-methacryloxytrimethoxysilane 2011.
μm aluminum hydroxide powder 3.000I! was added and dispersed using a co-kneader.

Next, 1,000.9 methyl methacrylate/methyl acrylate resin powder (average molecular weight 100,000) with a particle size of 20 mesh or less and a ratio of 9:10 was added, and the mixture was heated at 60°C.
After kneading and aging for 60 minutes, the mixture was cooled to room temperature to obtain a hard rubber clay-like molding material.

Next, cut out 500I from this molding material with a cutter knife, hold it at 120℃ for 30 minutes under pressure of 50 to 9/effl using a tray-molding compression mold, and make a size of 250× 15ωX O, got a tray from S country. This tray has a beautiful white marble-like transparency, and the Izotsu impact strength was measured using test pieces cut from this tray.JI
The heat distortion temperature (measured according to ASTM D-648) is 13.
It was 0°C.

Example 2 Trimethylolpropane trimethacrylate soo! !
, Styrene 500, F, di-t-butyl gloss oxide 1011 and γ-methacryloxytrimethoxysilane 20. 4.00 (l) of aluminum hydroxide powder with an average particle size of 3 μm was added to the mixed solution of P and dispersed in a co-kneader. Next, methyl methacrylate/styrene having a particle size of 20 mesh or less was mixed in a ratio of 7:3. Add 1,500.9 resin powder (average molecular weight 200,000) to 6
After kneading and aging at 0° C. for 30 minutes, the mixture was extruded and cooled to room temperature to obtain an elastic solid plate-shaped molding material. This molding material 5ooII was heated to 140°C using the same mold as in Example 1.
, held under pressure of 70 to 9/- for 20 minutes and 25c! n
×15 cr! A tray containing XX0.75 was obtained. This tray had a white, oak-like transparency and a moxibustion feel, and a test piece cut from this tray had an Izot impact strength of 3 mm/α and a heat distortion temperature of 120°C.

(Effects of the Invention) The present invention is an excellent method that makes it possible to easily produce beautiful and highly heat-resistant natural stone preparations regardless of their shape.

Claims (1)

[Claims] 1. Monomer (A) containing polyfunctional (meth)acrylate as an essential component, methacrylic resin powder (B) derived from a monomer containing methacrylic acid ester as an essential component , a curing agent (C) of the monomer (A), an inorganic filler (D), and if necessary a coupling agent, a coloring agent, and a reinforcing material are kneaded and aged at room temperature or under heating below the curing temperature. A method for producing natural stone preparations, which is characterized by molding and hardening a clay-like or solid molding material at room temperature by heating it under pressure.