JPS60106841A - Flame-retarding thermoplastic resin particle and its production - Google Patents

Abstract

PURPOSE:To produce the titled expandable resin particles excellent in weather resistance, solvent resistance, etc., by allowing vinyl chloride resin particles suspended in water to adsorb a vinylaromatic monomer, polymerizing this monomer and impregnating the resin particles with a blowing agent. CONSTITUTION:(A) 50-80pts.wt. core-forming resin particles (particle diameter of about 0.5-10mm.) comprising a vinyl chloride polymer are dispersed in an aqueous medium, (B) 50-20pts.wt. vinylaromatic monomer (e.g., styrene or vinyltoluene) is added to the resulting suspension to allow the resin particles to adsorb the monomer, and the monomer is polymerized within the particles in the presence of a polymerization catalyst. About 3-40wt%, based on component A, normally liquid vaporous or liquid blowing agent (e.g., propane, cyclopentane, or methyl chloride) is added and infiltrated into the resin particles to form expandable resin particles. These resin particles can be easily formed into primary expanded particles of a low specific gravity;

Description

DETAILED DESCRIPTION OF THE INVENTION This invention (4) relates to flammable thermoplastic resin particles and a method for producing the same.

More specifically, the present invention provides primary foamed particles that are flame retardant, have excellent weather resistance, oil resistance, and solvent resistance, and can be made with low specificity without using remanufactured A or the like. When molded in a mold using foam particles, each foam particle has good fusing properties and a foam molded product of any shape can be obtained. It is intended to provide resin particles.

Molded bodies made of thermoplastic resins, especially foam molded bodies, are used as heat insulating materials or heat retaining materials.

In particular, those containing a foaming agent and using J4+Tadze foam injectable resin particles as a 41 material can outperform ordinary foam molded products, so they are suitable for use in high-quality clay ware and buildings. flooring,
Widely used as heat/cold insulation material for tanks. However, compared to non-foamed molded products, foamed molded products made from hot surface injection resins tend to burn when exposed to static electricity or flame, and are more likely to burn. For this reason, it is desired to provide foamed molded articles with heat-extinguishing properties or self-extinguishing properties. ζ゛, research is being widely conducted to obtain flame-retardant optical foam molded articles by adding an IF fuel to thermoplastic resins.

A highly combustible thermoplastic that is self-extinguishing at a low ratio and can be foamed by adding a flame retardant and a foaming agent to particulate polystyrene resin as a raw material for obtaining foam molded products of arbitrary shapes.
+, resin particles are known. However, the foam molded product obtained by foam molding using this material has weather resistance p m
It had the disadvantage of being inferior to rt chemical properties and 1lfJ oil properties.

On the other hand, a foamed molded product made from agglomerated vinyl μ resin is known as a flame-retardant, chemical- and oil-resistant foamed product. This vinyl chloride 1vK4 fat thread foam is currently being manufactured by the press-expanding method, but a method for filling expandable particles into a mold to make a foam molded product has not yet appeared. This is the reality. This is because even though it was possible to foam vinyl chloride resin, it was not possible to form a molded product due to the difficulty in adhesion between vinyl chloride/l/based resins when heat molding. It is.

However, instead of performing this molding by thermoforming, it is known to form a molded article by coating the surface of the resin with an eyebrow agent or a thermoplastic resin capable of heat-N.

However, the processing temperature for vinyl chloride μ alone jM combination is about 160°C, which requires a very high temperature to perform foam molding, and it is difficult to mold at the usual 1ML degree of about 100°C. Rarely. The foamed molded product made of vinyl chloride/l' star mixture contained plasticizers and the like, and was not desirable in terms of growth.

The inventors of this invention conducted intensive research in order to solve the above problem, and as a result, they determined that vinyl chloride/I/, & coalescence or chloride and two-μ co-arashi coalescence were used as the core material resin. By substantially absorbing the vinyl ρ aromatic monomer in the particles and incorporating the monomer in the particles, the resulting particles have flame retardancy, weather resistance, and oil-friendly properties.

It is possible to impart solvent properties, and when impregnated with a blowing agent, it can be superior to the primary foamed particles with a low ratio without using a plasticizer. Money! In the PJIt molded in the U, 11% of each -5tr foam 1:11L was poured, and it was confirmed that the foamed particles that could be made into a foam molded product with a well-formed and lazy shape were obtained. , and this invention was completely completed.

That is, the present invention comprises 50 to 80 direct quantities of core resin particles made of a polyvinyl polymer, and a vinyl polymer polymerized with 50 to 80% of the core resin particles comprising a polyvinyl polymer having a vinyl aromatic content substantially absorbed in the particles. An illusion consisting of 50 to 20 aromatic combinations [P
1'''J foamable foam, which consists of thermoplastic resin particles containing a foaming agent that is gaseous or liquid at room temperature;
flammable thermoplastic resin particles and core material resin particles consisting of vinyl chloride/l/49 combination. Let me rR3, K H'! Add vinyl aroma D: 'monomer 50 to 20 parts to DJ M, and absorb it into the particles in a dithering manner, polymerize in the presence of a polymerization catalyst, and in the gap, before polymerization, stone At the time of the match or after the nails are completely spun, W;
The present invention provides a method for producing explosive thermoplastic particles comprising adding Jk to obtain expandable particles containing expanded 4j.

In the present invention, it is necessary to use vinyl chloride/L/submerged particles as the core resin particles, and to texture the vinyl chloride negative group hexamer in the resin. If you simply mix the plasticized vinyl μ-merged product and the vinyl male-contained resin combined product, then if you mold this mixture using a conventional method such as injection molding or injection molding, the resulting molded product will be different. When a foaming agent is added to the mixture of vinyl chloride and vinyl chloride (divided into a combined layer and a vinyl fragrance & storm combined layer), a molded product with a length of 11 mm is formed, and a foaming agent is added to the mixture. Kamie particles cannot be photographed.

As a vinyl chloride casing of such core material iaj iIM,
If a PVC vehicle is combined with a polarized vinyl co-contact base)
I can stay. Hinyl chloride Kyohongo P! ``As'' vinyl muide, styrene, methyl methacrylate, acrino V
(-g-methyl, vinylidene chloride, ethylene, diethyl male), and copolymers of 12 vinylidene and chloride.

When the particles of the present invention are prepared using vinyl chloride melon agglomerates or vinyl chloride lv melon agglomerates as core material resin particles, the impact resistance is poor. It can also be mixed with a polymer or vinyl chloride copolymer. When such a subaggregate is used, a portion of the vinyl μ aromatic monomer is grafted onto the subaggregate, and a homogeneous mixture can be obtained, which is preferable.

As such polyolefin thread aggregate, polyethylene,
Examples include holin-o-robirene, ethylene-vinyl acetate co-polymer, chlorinated polyethylene, cross-μ sulfonated polyethylene, chloro7°lene, polyligten, etc., and these are preferably used alone or in combination of two or more. Polyethylene and ethylene-vinyl acetate typical combinations are used.

The polyolefin polymer used is less than 30 weight 1# as core resin particles. If it exceeds 80 nails, the tactile properties will be impaired, which is not preferable. - In order to quickly absorb the vinyl μ aromatic monomer added in this invention, a particulate core resin is used. The size of the particles is preferably spherical, oblate, or pellet-shaped with a diameter of 0.6 to 10 cm.

In order to obtain the flame-retardant thermoplastic resin particles of the present invention, a vinyl μ aromatic monomer is absorbed into the core resin particles. Such vinyl μ aromatic monomers include styrene, α-methyp-styrene, ethylstyrene, vinyltoluene, and vinylxylene.

In-propiμ xylene solution alone or a mixture of two or more types, and monomers that can be co-combined with vinyl aromatic monomers containing 50% by weight or more of these vinyl aromatic monomers, such as acrylonide +7 / It may also be a mixture with V, methyl acrylate, methyl acrylate, etc.

The vinyl aromatic monomer is used so that the resulting twistable thermoplastic resin particles have a composition of 50 to 20 vinyl μ aromatic groups and 50 to 80 units of core resin.

The vinyl μ aromatic monomer absorbed into the core resin particles is polymerized in the particles to obtain thermoplastic resin particles that form the base 7 of the expandable particles of the present invention.

If the above core material resin is less than 60M flight warning l9, then
If the value exceeds 80 points, the foaming properties will deteriorate, which is not preferable.

To thoroughly understand the method for obtaining combustible thermoplastic resin particles of the present invention, particles of core material resin are first prepared. In the case of particles of vinyl chloride μ-wheel-coat aggregate or vinyl chloride copolymer, they are used as they are as the core resin. Vinyl chloride polymer and polyolefin thread'! In the case of using a resin mixture with a paving body, for example, after sufficiently mixing them, they are supplied to an extruder, and the resins are melted and uniformly kneaded in the extruder.

After mixing, the extruder is placed at the tip of the extruder and extruded into a large number of slender bodies through a 6' die. Nasu.

The core resin particles obtained as described above are suspended in an aqueous medium containing a dispersant. Examples of the dispersant include partially saponified polyvinyl alcohol, polyacrylate,
Polyvinylpyrrolidone, power ρ boxymethyρose~rose,
In addition to organic compounds such as methyrho7μ rose, stearate psium, ethylene bisstearamide, calcium pyrophosphate, calcium phosphate, R acid μsium, rehydrated magnesium, magnesium phosphate, birolin tA moxibustion magnesium, and magnesium oxide. An inorganic compound made of fine powder that is soluble in water is used. These dispersants are generally used in an amount of 0.01 to 51 ttlc'% based on water.

Next, a vinyl aromatic monomer and a polymerization catalyst are added to the separated core resin particles.

Examples of such polymerization catalysts include benzyl peroxide and tert-butyl perbenzoate.

fluoroyl peroxide, tert-butylperoxy-2-ethylhexane), organic peroxyride exclusively for tert-butylperoxide, azobisisobutyronitrile, azobisdimethylpaleronite 1)/L/f
No. 9 azo compound behavior can be mentioned. These catalysts may be used alone or in combination of two or more.

These polymerization catalysts can be used by being dissolved in the vinyl μ aromatic monomer or in a solvent such as benzene, toluene, xylene, etc. that does not harm the polymerization.

In order to prevent the formation of homopolymers of vinyl aromatic monomers and to prevent them from polymerizing on the surface of the core resin particles, it is possible to gradually add vinyl aromatic monomers to the suspension liquid little by little. It's delicious.

The vinyl resin suspended in the suspension is quickly absorbed into the core resin particles and polymerized in the core resin particles, resulting in the expansion of the expandable particles of the present invention. Thermoplastic resin particles serving as a base are obtained.

If the absorption of the A+4 resin in the resin is incomplete, when pre-foamed to form expandable particles, the foamed state will be cored and non-uniform in shape (dumpling-like).

On the other hand, Prediction 9 when absorption is completely rejected by %>:
'a Foamed particles are coreless and particle-shaped.

The above heat is acceptable! )17i! The resin particles themselves are flame retardant and have a good ability to retain the foaming agent inside, and when made foamable, each particle melts well during foam molding, so it can be formed into any shape. Foam molded products can be obtained, and also &
It is immersed in JL nature. Furthermore, since no flame retardant is used, deterioration in weather resistance can be minimized (generally, when a flame retardant is mixed in, the weather resistance is significantly reduced).

In this general category, zinc stearate, zinc ricinol, and μsium stearate are used as stabilizers to improve the thermal stability of engineered vinyl resin.

One or more of calcium thurate, tin nateate, tin maleate, tin thurate, dibutyltin laurylate, zinc stearate, lead stearate, lead naphthenate, or the like can be added in combination. It is preferable to use such a stabilizer in an amount of 0.05 to 6% by weight based on the core material resin consisting of vinyl chloride=/l/polymer. If the amount is less than 0.05% by weight, the stability effect will be poor, and if it exceeds 6% by weight, the physical properties will deteriorate. Furthermore, a spreading agent such as polybutene may be used to improve the cross-contamination between the vinyl chloride resin and the thermoplastic resin. Such spreading N agent is used in the range of 0.1 to s, oxiitφ for the agglomerated vinyl/l/resin. It is also possible to use other layer coloring agents, anti-banding agents, etc. as appropriate.

In order to make the thermoplastic resin particles foamable,
A blowing agent is added. As the foaming agent, one that is gaseous or liquid at room temperature is used. Such blowing agents include propane, n-butane, 1-butane, n-pentane, i-
Pentane, n-hexane and other aliphatic torpedoes, V-clopentane, cyclohexane exclusive, λ-type aliphatic hydrogen chloride, methyl chlorophyte, ethylchlorine, C-do, dichlorodifluoromethane, chlorosif~olomethane, trichloro Halogenated hydrocarbons such as fluoromethane can be used. These photo-14 agents are generally contained in a ratio of 8 to 40 Ai relative to the thermal plastic resin particles of the paste.

1^ In order to make the plasticity particles contain the above-mentioned foamed water,
The process of obtaining the particles, ie vinyl aromatic! i) At the same time when impregnating the group monomer, or during the polymerization when the polymer on the core is polymerized, or when the polymerization of the polymer described in 8iI is completed, excellent flame retardant thermoplastic resin particles are obtained. added after.

If a blowing agent is added before polymerization, the blowing agent is added to the suspension of core resin particles with or without dissolving in the vinyl aromatic monomer. When a flame retardant is added during polymerization, it is preferably used by dissolving it in the vinyl aromatic monomer and dispersing it in an aqueous suspension after completion of the polymerization. Generally, when adding a blowing agent, it is preferable to impregnate the foam under pressure using a pressure-resistant container.

The expandable, highly flammable thermoplastic resin particles obtained by the present invention can easily obtain primary expanded particles with a desired expansion ratio, and these secondary expanded particles can be used to mold in a molding die. In this process, a foam of any shape can be obtained with good fusion properties of each secondary foamed particle, and the foam molded product obtained by foam molding has excellent flame retardancy, weather resistance, and chemical resistance. , oil resistance has been added.

The lla flammable thermoplastic resin particles of this invention are i@chemical.

It has excellent solvent resistance, and contains seeding, NiLV polymer, and vinyl chloride copolymer, so chemical resistance and 1Ilit solvent resistance are improved, and there is no need to use flame retardants, so it is difficult to use. The deterioration of drinking resistance due to fuel is minimized, and furthermore, primary foamed particles with a desired expansion ratio can be easily obtained, and these secondary foamed particles can be used to mold in a mold. In this process, each sub-expanded particle has good fusion properties, and a foam having an arbitrary shape can be obtained. Furthermore, since there is no need to use a plasticizer during this foaming process, the plasticizer poses hygienic problems, and various other remarkable effects are exposed.

Next, the present invention will be explained with reference to Examples.

5A Example 1 100 parts by weight of a polymerized vinyl polymer (average degree of integration 1000) and 8 parts by weight of lead stearate were added, heated and kneaded in an extruder, and extruded to an average width of 2 mm in diameter.

A particulate core material resin having an average length of 4 cylinders was obtained.

Nucleus resin particles 12001 obtained above! and 2,000 ml of water in a blood mixer with an internal volume of 51. Metathesized magnesium birophosphate 4.8J, dodecylbenzenesulfonic acid) IJ
The cells were suspended in an aqueous medium containing 17 μm of 2% aqueous LitO,P. In this suspension, there is a
O'ir't 2.8g, tert-buti fi//<
-ben yx -) 0.21 t styrene mono ¥80
Add the 01111C1B-decomposed IJcrM solution and add 150
The temperature was raised to 90° C. under mtp at r-1)-m-. Polymerization was continued for 7 hours at a temperature of 90°C, and then at a temperature of 120°C.
The temperature was raised to tm degree (°C), polymerization was carried out for 2 hours, and then cooled to obtain vinyl chloride/L/m combined particles containing a styrene polymer inside.

The obtained vinyl chloride/1/window composite was fed into an extrusion machine for 1J18, and the thickness IITlm was measured by the guide attached to the tip of the extruder.
When extruded into a sheet, no layer separation occurred. Even when this sort was brought close to a candle, it did not burn out at all, so the particles obtained above were orchid-added vinyl chloride/I' polymer particles.

The above vinyl chloride coagulated particles tooog were suspended in an aqueous solution obtained by adding Dode V/L/benzene μ sodium phosphate 6011 to water aooog in the above nail combiner. While stirring the thread, 200 g of n-butane was injected into the thread, impregnated with 1i41 at 6:00 at a temperature of 70°C, and cooled to a temperature of 20°C. It was taken out from the tllllt self-polymerization stand, dehydrated 11i, and burnt.

When the obtained TL was heated for 20 seconds at a dlA degree of 90"C, it was foamable flame-retardant vinyl chloride fish coalescing particles that expanded 88 times.

The ζ-subexpanded particles obtained above have a length of 800 mm. mm.

Closed trout ti with a mold cavity of width 100mm + height 100M
Li1) was filled in the gold medallion, which could not be sealed, and foam molding was performed using water vapor. When the obtained foamed molded product was made of 11 apricots, each particle had an extremely high Mn2 ji! It showed M properties. When a candle was brought close to this foamed molded article and the state of combustion was observed, no combustion occurred.Example 2゜'iA In Example 1, core material resin particles 1400L styrene monomer 6017. benzoate/L//(-oxide 2.1g, tert-butyμ)(-benzoate 0.1
5.9, except that the same conditions were used for impregnation with blood and foaming agent, and the same tests were also conducted.

The particles obtained are flammable, υ, and 2 at an i temperature of 90°C.
Heat for 0 seconds and foam to 80 times the original size.

It also had excellent fusion properties, possible flame retardant chloride and 2μ polymer particles.

Example 8゜9! In Travel Example 1, core material resin particles 1600F1, styrene monomer 400.5', benzyl peroxide 1.4g, tert-butyl perbenzoate 0.19
Polymerization and blowing agent impregnation were carried out under the same conditions except for the following changes, and repeated tests were conducted.

The obtained particles were imparted with inkstone properties, and 9
When heated for 20 seconds at a temperature of 0'C, the foam expanded nine times, and as a result of foam molding using these particles, a foamed molded product in which each particle was well fused was obtained.

Example 4. ~5゜ Same as Example 1, except that the vinyl chloride polymer was replaced with an ethylene-vinyl chloride copolymer containing 5 mm% of ethylene'lk, and a vinyl chloride IvJ11 polymer and a rolled ethylene polymer were used, respectively. Polymerization and blowing agent impregnation were carried out under the same conditions and the same test @foam molding was carried out.

As a result, primary foamed particles expanded 41 times and 45 times, respectively, were obtained by heating for 20 seconds.

As a result of foam molding using these secondary foamed particles,
It was a foamed molded product with no shrinkage in which each particle was well fused.

This foam molded product did not burn at all.

Example 6 In Example 1, 1500 g of core resin particles and 5009 g of styrene monomer were added. Benzoyl peroxide 1.81
Impregnation with nail metal and a foaming agent was carried out under the same conditions except that % tert-glybur benzoate o and i were changed to 5 g.

When the obtained particles were heated at a temperature of 90° C. for 20 seconds, primary foamed particles expanded 15 times in size were formed. This-
As a result of performing foam molding using the sub-expanded particles, a foam molded article was obtained in which each particle was clearly fused together.

Claims (1)

[Claims] 1. Core material resin particles 50 to 8 made of vinyl chloride YVM coalescence
03ijjt and 50 to 20% by weight of a vinyl aromatic polymer polymerized with the vinyl aromatic senomer substantially absorbed into the particles, and a foaming agent that is gaseous or liquid at room temperature. 1j) 1 particle of a flammable thermoplastic tree containing: 2. Core material resin particles consisting of vinyl chloride/1/nail combination 50~
80 Egakibe is suspended in an aqueous medium, and vinyl aromatized Zuma-50-2 (lfit part) is added to the liquid and substantially absorbed into the particles, and the presence of a mixing catalyst is added. Mix with a knife, and at that time, polymerize the gas or liquid foaming agent at room temperature.
A method for producing flame-retardant thermoplastic resin 111f particles, which comprises obtaining resin particles containing a blowing agent by adding a blowing agent at the time of heavy metallization or after completion of polymerization.