JPS63221151A - flame retardant artificial marble - Google Patents

Abstract

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

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides aluminum hydroxide powder-filled polymethyl methacrylate-based artificial marble having excellent flame retardant performance and its! 81 Concerning the manufacturing method.

(Prior art) Polymer molded products whose main component is methyl methacrylate filled with aluminum hydroxide powder have a deep and beautiful surface, excellent mechanical strength, excellent weather resistance, and corrosion resistance. Due to its properties such as excellent durability and flame retardancy, artificial marble products are used in various tabletops, countertops, bathroom vanities, sinks, bathtubs, shower trays, waterproof pans, flooring materials, wall materials, Widely used for partition boards, arts and crafts, etc. The flame retardancy of this artificial marble is due to the fact that the aluminum hydroxide powder contained as a filler contains 34.5% of multiple bound water, which causes a rapid dehydration decomposition reaction at around 200°C. This is to absorb multiple amounts of heat at the same time, and if aluminum hydroxide powder is added to ordinary flammable plastic, it will meet the UL standard 94. It is also possible to impart flame retardancy that passes V-0. However, if a large amount of aluminum hydroxide powder is filled in an attempt to achieve a higher degree of flame retardancy, the filling becomes opaque and loses its sense of depth. If used in combination, the properties such as depth, heat resistance, weather resistance, corrosion resistance, and strength will deteriorate, so it is possible to maintain the excellent properties of polymethyl methacrylate artificial marble filled with aluminum hydroxide powder, while maintaining the advanced 81M performance. It is difficult to assign.

(Problems to be Solved by the Invention) The present invention solves the problem without impairing the excellent properties of polymethyl tafrylate artificial marble filled with aluminum hydroxide powder.
This is intended to provide a higher degree of flame retardant performance.

(Means for Solving the Problems) The present inventors have made intensive studies to solve the above problems, and as a result, have completed the present invention. That is, a polymer whose main component is vinyl chloride-vinylidene chloride copolymer resin in an amount of 5 to 40% by weight based on the amount of a in the resin phase and methyl methacrylate in an amount of 95 to 60% by weight based on the total amount of the resin phase. Artificial marble consisting of 20 to 80 parts by weight of a resin phase consisting of and 80 to 20 parts by weight of aluminum hydroxide powder (however,
5t is 1001ffi parts. However, while maintaining the excellent properties of polymethyl methacrylate artificial marble,
They discovered that it has a high degree of flame retardancy.

Such artificial marble can be manufactured by various methods, but preferably from 5 to 4, based on the total amount of syrup.
0% vinyl chloride-vinylidene chloride copolymerization 4! lI
1 and 20 to 80 parts by weight of syrup consisting of 95 to 60% by weight of a polymerizable monomer mainly composed of methyl methacrylate, and 80 to 20 parts by weight of aluminum hydroxide powder.
! ff in a total amount of 100 parts by weight, and the mixture is introduced into a mold and molded and hardened.

The polymer containing methyl methacrylate as a main component in the present invention refers to a polymer of polymerizable monomers containing methyl methacrylate as a main component. The polymerizable monomer containing methyl methacrylate as a main component herein refers to methyl methacrylate alone or less than 50% by weight of methyl methacrylate substituted with other α,β-unsaturated compounds. The α,β-unsaturated compound that can substitute for methyl methacrylate is not particularly limited as long as it is compatible with methyl methacrylate and can be copolymerized with methyl methacrylate; examples of such compounds include acrylic acid and methacrylic acid. , esters of -6 alcohols having 1 to 18 carbon atoms and acrylic acid, esters of -6 alcohols having 2 to 18 carbon atoms and methacrylic acid, olefinic nitriles such as acrylonitrile and methacrylonitrile, acrylamide and methacrylamide, etc. Olefinic amides, aromatic unsaturated compounds such as styrene and α-methylstyrene, functional monomers such as vinyl esters such as vinyl ester and vinyl benzoate, and acrylic and methacrylic acids with ethylene glycol and polyethylene. glycol, polypropylene glycol,
1,3-butanediol, neopentyl glycol, 1
, 6-hexanediol, trimethylolethane, trimethylolpropane, tetramethylolmethane, pentaerythritol, dipentaerythritol, and other polyesters with polyhydric alcohols such as divinylbenzene, diallyl phthalate, triallyl cyanurate, etc. Examples include, but are not limited to, monomers.

Two or more types of α,B-unsaturated compounds that can substitute for methyl methacrylate may be used. Furthermore, the polymerizable monomer whose main component is methyl methacrylate can be partially polymerized in advance and used as a polymer solution, and it is also possible to dissolve polymers other than vinyl chloride-vinylidene chloride copolymer resin. It is also possible to use it as a polymer solution. However, in this case as well, the composition of the polymer solution is such that methyl methacrylate accounts for 50% by weight or more in terms of monomers.

The vinyl chloride-vinylidene chloride copolymer resin used in the present invention is a blended product with a polymer whose main component is methyl methacrylate, so that it gives a sense of depth to the artificial marble.
It is necessary to be transparent or semi-milky, and most preferably transparent. The composition of vinyl chloride-vinylidene chloride copolymer resin having such properties varies depending on the composition of the polymer whose main component is methyl methacrylate, but the vinyl chloride-vinylidene chloride copolymer resin composition has a vinyl chloride content of 50 to 50%. The intrinsic viscosity measured at 30°C using tetrahydrofuran as a solvent is 0-1 to 1.0 dl/g, preferably 0.2 to 0.5 dl/9. For example, when the polymer containing methyl methacrylate as a main component is a methacrylic resin and the vinyl chloride-vinylidene chloride copolymer resin composition has a vinyl chloride content of 59.8 ffiM%, the blended product is transparent.

The amount of vinyl chloride-vinylidene chloride copolymer resin added to the polymer mainly composed of methyl methacrylate is 5 to 40% by weight, preferably 10% by weight, based on the aeration of the resin phase.
and 25% by weight.

If the amount of vinyl chloride-vinylidene chloride copolymer resin added is less than 5% by weight, a high degree of oxidation will not be achieved;
If it exceeds 0% by weight, the properties such as heat resistance and weather resistance of the artificial marble product will deteriorate, which is not preferable.

There are no particular limitations on the aluminum hydroxide powder used in the present invention, but the particle size is 200 μm or less, preferably 10 μm or less, more preferably 50 μTrL or less. The amount of aluminum hydroxide powder added to the resin phase is naturally determined by the depth, specific gravity, hardness, strength, heat resistance, flame retardance, price, etc. of the desired artificial marble product, but it is based on the total amount of both. 20 to 8
G weight %, preferably 40 to 75 weight %. If the amount of aluminum hydroxide powder added exceeds 80% by weight, the depth of the artificial marble product will be lost and properties such as strength will also deteriorate, which is not preferable. If the amount added is 20% by weight, the properties such as hardness, heat resistance, and flame retardance will be poor, which is not preferable.

In the present invention, there are no particular limitations on the method of mixing each component to form a product. For example, a polymer mainly composed of methyl methacrylate and a vinyl chloride-vinylidene chloride copolymer resin can be mixed under melting conditions, and aluminum hydroxide powder can be further added thereto and mixed to shape the mixture. It is also possible to obtain the product by molding. That is, a syrup made by dissolving a vinyl chloride-vinylidene chloride copolymer resin in a polymerizable monomer mainly composed of methyl methacrylate,
A product is obtained by introducing a slurry containing aluminum hydroxide powder into a mold and molding and hardening it.The cast molding method has low manufacturing costs and easy operation, and also has the stain resistance of artificial marble products. It has the advantage that it is easy to introduce a crosslinked structure to improve heat resistance. Note that there are no particular restrictions on the method of obtaining the syrup or slurry. For example, vinyl chloride-vinylidene chloride copolymer resin is added to a polymerizable monomer mainly composed of methyl methacrylate with stirring, and the mixture is heated or cooled. Syrup can be made by continuing stirring until it dissolves, and syrup and aluminum hydroxide powder can be mixed in a tank equipped with a stirrer or in a kneader.
This can be done using The obtained slurry may be directly introduced into a mold and molded and cured, but before that, it may be subjected to a thickening operation or a part of the curing reaction is performed to form SMC, BMC, etc., and then introduced into a mold and molded and cured. It is also possible to do so. Therefore, the molding hardening according to the present invention is not limited to molding using a closed cell device, a covered open cell device, an open mold, etc., but also molding using a continuous pour molding device, and the above-mentioned SMC, BMC, etc. using a compression molding device, an injection molding device, etc. It also includes the molding of

In addition, in cast molding, the amount of vinyl chloride-vinylidene chloride copolymer resin added is 5% by weight based on the total amount of syrup.
If it is less than 40% by weight, the slurry will have no viscosity and will have difficulty flowing when introduced into a mold, or the aluminum hydroxide powder will settle and separate. If it exceeds 40% by weight, the slurry viscosity will be high and it will not be possible to mix or introduce it into a mold. This is not desirable because it makes it difficult. Furthermore, if the amount of aluminum hydroxide powder added to the total seedlings of syrup and aluminum hydroxide powder exceeds 80% by weight, the viscosity of the slurry will increase, which is not preferable.

The curing method according to the present invention is not particularly limited, and includes, for example, heating in the presence or absence of a radical polymerization initiator, a method using a so-called redox system consisting of a radical polymerization initiator and an accelerator, and irradiation with ultraviolet rays or radiation. This method can be carried out using any method, but is not limited to these methods. When cast molding is carried out, it is usually carried out by heating to a temperature of 20 to 130°C, preferably 50 to 90°C, in the presence of a radical polymerization initiator.

Examples of radical polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'azobis(2,4-dimethylvaleronitrile), diisopropyl peroxydicarbonate, di(methoxyisopropyl), etc. ) peroxydicarbonate, t-butylperoxyneodecanoate, lauroyl peroxide, benzoyl peroxide, and 2,2-bis(t-butylperoxy)butane. 0.005 to 3% by weight, preferably 0.01%
It is used in an amount of 1% to 1% by weight. It is also possible to use two or more types of radical polymerization initiators in combination.

In addition to the above-described aluminum hydroxide powder, methyl methacrylate-based polymer, and vinyl chloride-vinylidene chloride copolymer resin, the artificial marble product of the present invention may contain, if necessary, within the range that does not impair physical properties. Polymers other than small polymers mainly composed of methyl methacrylate and vinyl chloride-vinylidene chloride copolymer resins are
Methyl methacrylate can be added to the resin composition excluding the vinylidene chloride copolymer resin so long as it does not become less than 50% by weight in monomer terms, and fillers, dyes and pigments, reinforcing materials, and modifiers other than aluminum hydroxide powder can be added. It is also possible to contain a qualifier, a stabilizer, a molding agent, a lubricant, a polymerization accelerator, a polymerization initiator residue, a polymerization regulator residue, and the like. For the purpose of further improving the flame retardant performance, it is also possible to add antimony compounds such as antimony trioxide, antimony trichloride, and triphenylantimony, phosphorus compounds, and halogen compounds within a range that does not impair the properties.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited in any way by these Examples.

Examples 1 to 5 The best vinyl chloride-vinylidene chloride copolymer resin shown in Table 1 (Geon 222.B, F, Goodrich Ch
ell, Co, Ltd.

An example of the analysis value of the resin composition is vinyl chloride content of 59
．． 8ffifQ%, 3 using tetrahydrofuran as solvent
An example of intrinsic viscosity measured at 0°C is 0.375 dl/g
) was dissolved in methyl methacrylate and trimethylolpropane trimethacrylate of ω shown in Table 1 to obtain syrup. To 40 ffiffi parts of this syrup, 60 parts of aluminum hydroxide powder (Hisilite H-310, manufactured by Showa Denko ■), 1.5 parts by weight of antimony trioxide, 0.1 part by weight of lauroyl peroxide, 1,1-bis(
0.1 part by weight of t-butylperoxy>3.3.5-trimethylcyclohexane was added to obtain a slurry.

A soft polyvinyl chloride gasket arranged in a U-shape,
The above slurry was poured into a cell assembled between two glass plates, immersed in a 60°C water bath for 5 hours, and then held in a hot air oven heated to 120°C for 2 hours to polymerize. It was opened to obtain an artificial marble plate with a thickness of 12M.

All of these had a beautiful surface finish with an excellent sense of depth.

In addition, in a 500-hour accelerated exposure test using a sunshine weather meter, no changes were observed by visual inspection;
Even in the 0 hour accelerated exposure test, only slight changes were observed in Example 5.

The oxygen index was measured using J15K-7201 on an artificial marble plate having a thickness of 3 ram cast by the same method. From the oxygen index shown in Table 1, it can be seen that the artificial marble of the present invention has excellent flame retardant performance.

Comparative Example 1 Methacrylic resin (Parabeads HR, Kyowa Gas Chemical Industry @
Artificial marble slabs were obtained by the same method as in Examples 1 to 5, except that 40 parts by weight of syrup was used, in which 20% by weight of 20% by weight (manufactured by the manufacturer) was dissolved in 75% by weight of methyl methacrylate and 5% by weight of trimethylolpropane trimethacrylate. . The oxygen index measured by the same method as Examples 1 to 5 was 31.

Table 1 Comparative Example 2 The same vinyl chloride-vinylidene chloride copolymer tree F45ffiffi% as in Examples 1 to 5 was added to 50% methyl methacrylate.
Slurries were prepared in the same manner as in Examples 1 to 5, except for using 1 part of 40ffiff syrup dissolved in 11% and 5% by weight of trimethylolpropane trimethacrylate. Ta.

Examples 6 and 7 Vinyl chloride-vinylidene chloride copolymer resin (Flehalon 5
PX105. Manufactured by Kureha Chemical Industry @, an example of the analysis value of the resin composition is that the vinyl chloride content is 76.6% by weight, and the intrinsic viscosity measured at 30°C using tetrahydrofuran as a solvent is 0.320 dl/g>20% by weight. methysistacrylate
Examples 1-
The same aluminum hydroxide powder as in No. 5 was mixed in the proportions shown in Table 2. 100 parts of this mixture [1 part of antimony trioxide]
．． 5ffiffi parts, 0.02 parts by weight of 2.2-azobisisobutyronitrile, and 0.2 [f parts of 2.2-bis(t-butylperoxy)butane] were added to obtain a slurry, from which the Artificial marble plates were obtained by the same method as in Examples 1-5. All of these exhibited beautiful surface properties with excellent depth. Further, in the same accelerated exposure test as in Examples 1 to 5 for 1000 hours, no visible change was observed, and the oxygen index was as shown in Table 2, indicating that the film had a high degree of flame retardancy.

Comparative Examples 3 and 4 The oxygen index of an artificial marble board obtained by the same method as in Examples 6 and 7, except that the same methacrylic resin as in Comparative Example 1 was used instead of the vinyl chloride-vinylidene chloride copolymer resin, was as follows: They were 31 and 33, respectively.

Table 2 (Effects of the invention) The present invention has been achieved by adding a vinyl chloride-nylidene chloride copolymer resin to a polymer molded product containing methyl methacrylate as a main component, that is, an artificial marble product, filled with aluminum hydroxide powder. , which aims to provide a higher degree of flame retardant performance.

Since aluminum hydroxide contains a large amount of bound water, artificial marble blended with aluminum hydroxide will have a certain degree of flame retardant performance. However, if the filling rate of aluminum hydroxide is increased in an attempt to impart higher flame retardant performance, the artificial marble becomes opaque and loses its sense of depth. In contrast, the method of adding the vinyl chloride-nylidene chloride copolymer resin of the present invention makes it possible to impart a high degree of flame retardancy without losing depth. Also, vinyl chloride
Unlike low-molecular-weight phosphorus-based or halogen-based retardants, vinylidene chloride copolymer resin does not impair the heat resistance, corrosion resistance, strength, etc. of artificial marble. Furthermore, when manufacturing the artificial marble product according to the present invention by a cast molding method, the syrup viscosity is Because of this, the slurry obtained by adding aluminum hydroxide powder becomes sticky, and the fluidity of the slurry is maintained at an appropriate level, making it easy to operate, and the aluminum hydroxide powder settles during molding. It also has the effect of not separating.

Claims (2)

[Claims] (1) Based on the total amount of the composition, the following (A) and (
An artificial marble comprising 20 to 80% by weight of a resin phase consisting of B) and 80 to 20% by weight of aluminum hydroxide powder. (A) 5 to 4.40 based on the total amount of resin phase
% by weight of vinyl chloride-vinylidene chloride copolymer resin. (B) A polymer based on 95 to 60% by weight of methyl methacrylate, based on the total amount of resin phase. (2) Syrup consisting of 5 to 40% by weight of vinyl chloride-vinylidene chloride copolymer resin and 95 to 60% by weight of a polymerizable monomer whose main component is methyl methacrylate, based on the total amount of syrup. 20 to 80 parts by weight of aluminum hydroxide powder and 80 to 20 parts by weight of aluminum hydroxide powder are mixed in a total amount of 100 parts by weight, and the mixture is introduced into a mold and molded and hardened.