JPH11148002A - Production of flame-retardant molded resin article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject molded article having improved flame-retardancy and containing red phosphorus satisfying the workability and safety by including a specific thermoplastic resin composition and red phosphorus and using a specific red phosphorus flame-retardant in the compounding of the red phosphorus. SOLUTION: The objective molded article is produced by using a resin composition containing (A) 90-99.9 wt.% of a thermoplastic resin composition containing (i) >=10 wt.% of an aromatic polycarbonate in the resin composition composed of the components A and B and, as necessary, (ii) a thermoplastic resin other than the component (i), (iii) a reinforcing filler and (iv) a flame- retardant other than the component B and (B) 0.1-10 wt.% of red phosphorus. A master pellet of a red phosphorus flame-retardant composed of 80-95 wt.% of a thermoplastic resin essentially composed of the component (i) and 5-20 wt.% of the component B and having a specific surface area of 8-80 cm<2> /g is used in the compounding of the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a flame-retardant resin molded product comprising a resin composition containing an aromatic polycarbonate resin and red phosphorus. Specifically, in such a production method, a thermoplastic resin substantially consisting of an aromatic polycarbonate resin and a specific ratio of red phosphorus, and using a master pelletized red phosphorus flame retardant having a specific specific surface area, The present invention relates to a method for producing a flame-retardant resin molded product which can improve the workability and safety in such production by blending red phosphorus and further improve the flame retardancy of the molded product.

[0002]

2. Description of the Related Art In general, resin compositions containing an aromatic polycarbonate resin have been used in a wide range of fields due to good mechanical properties and heat resistance. Along with this, the demand for flame retardancy to ensure their safety has become more severe. Generally, organic halogen-based flame retardants, organic phosphorus-based flame retardants, red phosphorus-based flame retardants, and the like are known. Among them, it is known that red phosphorus, which has been used for a long time, can be effectively made flame-retardant by adding a relatively small amount. However, red phosphorus is relatively unstable and ignites under high temperature or static electricity, mechanical shock, etc., therefore, a resin composition containing an aromatic polycarbonate resin having a high processing temperature includes:
Problems remain in safety and workability.

[0003] In order to solve the problem of red phosphorus, a red phosphorus flame retardant obtained by microencapsulating red phosphorus with a thermosetting resin and / or an inorganic material has been used.
For example, in JP-A-6-116473, it is used for producing a halogen-free thermoplastic resin composition comprising an aromatic polycarbonate resin, an impact-resistant vinyl aromatic copolymer and red phosphorus. However, even such a microencapsulated red phosphorus-based flame retardant falls under the category of dangerous substances of the Fire Service Law, and when producing a resin composition composed of an aromatic polycarbonate resin having a high processing temperature, it is safe. The problem of sex and workability still remained. For example, if the processing temperature is lowered to ensure safety, the dispersion of the various components in the resin composition becomes insufficient, and the original characteristics cannot be obtained. In particular, there were problems such as deterioration of appearance due to poor dispersion of red phosphorus and reduction in flame retardancy which is considered to be caused by such poor dispersion. Further, when safety is ensured by a method such as nitrogen purging, in a resin composition in which various kinds of raw materials are mixed, impurities generated from each raw material in the composition are hardly discharged from a vent, and the quality of the resin composition is reduced. There was a problem that caused the deterioration of. Further, in the production of various resin compositions, it is a burden on the production to perform safety management such as nitrogen purging for all of a large number of production apparatuses, and there is also a problem that sufficient safety cannot be ensured. Was.

On the other hand, as a method for further improving the workability and safety of a red phosphorus-based flame retardant, JP-A-5-194787 discloses a method in which red phosphorus particles are individually coated with fine magnesium hydroxide, and A red phosphorus-based flame retardant comprising granules in which the coated red phosphorus is supported on a thermoplastic resin is disclosed. This publication describes that the red phosphorus-based flame retardant is not a non-dangerous substance. However, in the red phosphorus-based flame retardant, it is necessary that the amount of magnesium hydroxide is as large as 20 to 150% by weight with respect to the red phosphorus as an appropriate composition ratio. When applied to a resin composition containing a resin, magnesium hydroxide degrades the thermal stability of the aromatic polycarbonate resin, and has disadvantages such as degradation of the resin during molding and insufficient strength of the resulting molded product. Was.

Japanese Patent Application Laid-Open No. 63-110254 discloses a method of adding red phosphorus having a limited shape, which is manufactured by a specific manufacturing method, to a polycarbonate resin or the like. No. 67467 discloses a method such as polynuclear encapsulation in which red phosphorus particles and inorganic particles are contained in a matrix of spherical thermosetting resin particles, but the workability and safety have not yet been sufficiently satisfied. .

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, contains red phosphorus satisfying workability and safety, and improves the flame retardancy of a molded product. An object of the present invention is to provide a method for producing a flammable resin molded product.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have obtained a flame-retardant resin molded product comprising a resin composition containing an aromatic polycarbonate resin and red phosphorus. In the production method, when red phosphorus is blended, 80 to 95% by weight of a thermoplastic resin substantially consisting of an aromatic polycarbonate resin and 5 to 20% by weight of red phosphorus
By using a master-pelletized red phosphorus-based flame retardant having a specific surface area of 8 to 80 cm ² / g, the intended workability and safety are satisfied and the flame retardancy of the molded product is reduced. The present inventors have found that a method for producing a flame-retardant resin molded article that can be improved can be obtained, and have reached the present invention.

The aromatic polycarbonate resin used as the component a in the present invention is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. The dihydric phenol used here is 2,2-
It is intended for bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], but a part or all of it may be replaced with another dihydric phenol. Other dihydric phenols include, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester and haloformate, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. Two or more aromatic polycarbonate resins thus obtained may be mixed.

In the present invention, the viscosity average molecular weight (M) is determined by adding 0.7 g of a polycarbonate resin to 100 ml of methylene chloride.
The specific viscosity (η _sp ) obtained from the solution dissolved at 0 ° C. was obtained by inserting it into the following equation. η _sp /C=[η]+0.45×[η] ² C [η] = 1.23 × 10 ⁻⁴ M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.1. 7)

In producing the aromatic polycarbonate resin having such a molecular weight, an appropriate molecular weight regulator, a branching agent, a catalyst for accelerating the reaction, and the like may be used.

The basic means for producing an aromatic polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to promote the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. As a molecular weight regulator, a terminal stopper such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol can be used. It is desirable to use. The reaction temperature is usually 0 to 40 ° C, and the reaction temperature is several minutes to 5 minutes.
Preferably, the pH during the reaction is maintained at 10 or more during the reaction.

In a transesterification reaction (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined ratio of a dihydric phenol and a branching agent are stirred with a carbonic acid diester while heating in the presence of an inert gas to form an alcohol formed. Alternatively, it is carried out by a method of distilling phenols. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, and is usually in the range of 120 to 300 ° C.
The reaction is completed while distilling off alcohol or phenols produced by reducing the pressure from the beginning. In order to promote the reaction, a catalyst used in the known transesterification can be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.

The aromatic polycarbonate resin (component (a)) has a viscosity average molecular weight of 10,000 to 50,000.
Are preferred, and those of 15,000 to 30,000 are particularly preferred. If the molecular weight is 10,000 or less, the impact resistance is reduced. If the molecular weight is 50,000 or more, the molding processability is reduced and a higher processing temperature is required, which is not preferable from the viewpoint of safety.

The thermoplastic resin other than the aromatic polycarbonate resin used as the optional component b in the present invention includes aromatic polyester resins, aliphatic polyester resins, vinyl thermoplastic resins, polyamide resins, and polyarylate resins. , A polyolefin-based resin, and a thermoplastic elastomer such as a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer. Such a thermoplastic resin can be blended as needed, and it can be used alone or in combination of two or more depending on the purpose. Among these thermoplastic resins, aromatic polyester resins such as polyalkylene terephthalate and vinyl thermoplastic resins can be preferably used in view of flame retardancy, processing characteristics, mechanical characteristics and the like.

The aromatic polyester resin used in the present invention is a homo or copolymer obtained by a condensation reaction between a dicarboxylic acid component and a diol component. Examples of the dicarboxylic acid component include, as main components, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and ester-forming derivatives thereof, and, if necessary, succinic acid, oxalic acid, adipic acid, and sebacic acid. It may also contain aliphatic dicarboxylic acids such as acids and their ester-forming derivatives. Examples of the diol component include ethylene glycol, 1,4-butanediol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol and the like and ester-forming derivatives thereof. Particularly preferred aromatic polyester resins are polyethylene terephthalate and polybutylene terephthalate, the molecular weight of which is not particularly limited, but having an intrinsic viscosity of about 0.4 to 1.2 measured at 25 ° C. using o-chlorophenols as a solvent. Is preferred.

Further, the polyester resin in the present invention is not particularly limited as long as it satisfies the above-mentioned conditions. For example, in the production method, when an initial oligomer is produced, an aromatic dicarboxylic acid is directly used. Or a transesterification reaction using an alkyl diester of an aromatic dicarboxylic acid. As the catalyst for the condensation reaction, any of Sb-based compounds, Ti-based compounds, Sn-based compounds, and Ge-based compounds can be used, and the ratio of the carboxylic acid group to the hydroxyl group in the terminal structure is also particularly limited. It is not something to be done.

The vinyl thermoplastic resin used in the present invention is, for example, acrylonitrile, methacrylonitrile,
Vinyl cyanide compounds such as chloroacrylonitrile; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and halogenated styrene; and methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and acrylic acid Polymers such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, and acrylate compounds such as 2-ethylhexyl methacrylate, and copolymers, or in the presence of a diene rubber , 2
Examples include graft copolymers obtained by polymerizing the above-mentioned vinyl monomers which are copolymerizable by at least one kind.
As the diene rubber used here, polybutadiene, polyisoprene, butadiene-styrene copolymer,
Butadiene-acrylonitrile copolymer and the like. The polymer, copolymer and graft copolymer may be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and may be a single-stage graft or a multi-stage graft. Absent. Further, it may be a mixture with a copolymer of only a graft component which is by-produced during the production.

Further, such a vinyl-based thermoplastic resin may be one having a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst at the time of its production. Further, in some cases, a polymer and a copolymer having a narrow molecular weight distribution obtained by a method such as anionic living polymerization or radical living polymerization, a block copolymer, and a highly stereoregular polymer or copolymer are used. It is also possible.

In addition, some of the vinyl thermoplastic resins of the present invention have a composite having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated. A composite rubber-based graft copolymer (hereinafter referred to as IPN) obtained by graft-polymerizing one or more of the above-mentioned vinyl monomers onto rubber.
Type vinyl polymer). Further, two or more kinds of thermoplastic graft copolymers may be mixed.

Among these, acrylonitrile-styrene copolymer (AS resin), butadiene rubber-reinforced acrylonitrile-styrene copolymer (ABS resin), butadiene rubber-reinforced methyl methacrylate-ethyl acrylate-styrene are preferred. Copolymer, butadiene rubber reinforced methyl methacrylate copolymer, butadiene rubber reinforced methyl methacrylate-styrene copolymer, and IPN type vinyl polymer. Among them, IPN-type vinyl polymer is defined as Metablen S-200 by Mitsubishi Rayon Co., Ltd.
It is commercially available under the trade name 1 or SRK-200 and is easily available. In such a butadiene rubber-reinforced vinyl thermoplastic resin, the form of the rubber particles may be any of a salami structure, a core-shell structure, a rod-like structure, a drop-like structure and the like, and the average particle diameter is also 0.01.
The particle size may be any of from 10 to 10 μm, but when importance is placed on the appearance, a smaller particle size is desirable. The particle size distribution may be single or two or more distributions may overlap.

In the present invention, as the reinforcing filler arbitrarily mixed as the component c, those which are filled in currently known resins can be used. Specific examples of the reinforcing filler include silica, diatomaceous earth, alumina, and the like. Zinc oxide, titanium oxide,
Metal oxides such as cerium oxide, calcium oxide, magnesium oxide, and iron oxide; alkaline earth metal salts of carbonic acid such as calcium carbonate, barium carbonate, and magnesium carbonate; calcium hydroxide, magnesium hydroxide, and aluminum hydroxide Hydroxide, alkaline earth metal salts of sulfuric acid such as calcium sulfate and barium sulfate, hydrotalcite, wollastonite, talc, clay, glass fiber, short glass fiber, glass flake, glass beads, mica, montmorillonite, sepiolite , Sericite,
Glass balloon, carbon fiber, metal-coated carbon fiber, metal fiber, short carbon fiber, heat-resistant organic fiber such as aramid fiber and polyarylate fiber, charcoal powder, metal powder, potassium titanate, carbon whisker, graphite and the like. Such reinforcing fillers can be used alone or in combination of two or more, depending on the purpose, such as compatibility between the strength and appearance of the molded product and compatibility between the strength and the low anisotropy of the molded product.

Among such reinforcing fillers, glass fibers,
Reinforcing fillers such as short glass fibers, glass flakes, glass beads, mica, wollastonite, carbon fibers, metal-coated carbon fibers, short carbon fibers, heat-resistant organic fibers, and metal fibers can be preferably used. Can be used which is surface-treated with a silane coupling agent or the like, and is particularly preferable for glass fibers, short glass fibers, glass flakes, glass beads, mica, and wollastonite.
By this surface treatment, the decomposition of the aromatic polycarbonate resin can be suppressed, and the adhesion between the reinforcing filler and the resin can be improved.

The silane coupling agent used herein may be any of an aminosilane type, an epoxysilane type, a vinylsilane type, a mercaptosilane type, and a ureasilane type. Particularly, the aminosilane type is preferably used for the hue and strength of the composition. In this respect, epoxysilanes can be preferably used in view of the strength of the molded product.

Further, the reinforcing filler is preferably granulated or bundled with a binder such as an acrylic resin, a urethane resin, an epoxy resin, and an unsaturated polyester resin, because it is easy to handle. For mica, talc, etc., granulation method 1
One example is a degassing compression method.

The flame retardant other than red phosphorus used as the d component arbitrarily mixed in the present invention is for the purpose of achieving both flame retardancy and appearance such as hue and gloss, which cannot be achieved by red phosphorus alone. It can be used preferably. As such a flame retardant, various known flame retardants can be used, and specifically,
Brominated bisphenol, brominated polystyrene, carbonate oligomer of brominated bisphenol A, copolymer and copolymerized oligomer of brominated bisphenol A and bisphenol A, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate,
Phosphate ester compounds such as octyl diphenyl phosphate, various currently known polyphosphate esters represented by polyphosphate esters described in JP-A-59-202240, potassium perfluorobutanesulfonate, sodium lauryl sulfate, diphenyl Sulfone-3
Various known metal salt-based flame retardants such as potassium sulfonate can be used. Further, heat-expandable graphite generally used as a flame-retardant aid, silicone powder, and the like can also be used as the d component.

In the present invention, when blending red phosphorus as a β component, the thermoplastic resin consists essentially of 80 to 95% by weight of a thermoplastic resin composed of an aromatic polycarbonate resin and 5 to 20% by weight of red phosphorus, and has a specific surface area of Used is a master-pelletized red phosphorus-based flame retardant of 8 to 80 cm ² / g.
Such a compounding method is the greatest feature of the present invention. As a result, such master pellets do not fall under the category of dangerous materials under the Fire Service Law and are non-hazardous materials, which ensures sufficient workability and safety when obtaining flame-retardant resin molded products. It becomes possible.

The red phosphorus used in the production of the master pelletized red phosphorus flame retardant is obtained by microencapsulating the red phosphorus surface using a thermosetting resin and / or an inorganic material in addition to general red phosphorus. Red phosphorus can be used. Further, the use of such microencapsulated red phosphorus is preferably used in order to improve safety and workability in the production of such a master pelletized red phosphorus flame retardant. Examples of the inorganic material used for such microencapsulation include magnesium hydroxide, aluminum hydroxide, titanium hydroxide, and the like.
Examples of the thermosetting resin include phenol / formalin-based resin, urea / formalin-based resin, and melamine / formalin-based resin. Furthermore, on those coated with such inorganic materials,
Red phosphorus or the like, which is formed by forming a coating using a thermosetting resin and is double-coated, can also be preferably used. The average particle size of red phosphorus is 1 to 100 μm, preferably 2 to 40 μm. There is an advantage that the smaller the particle size, the higher the impact resistance, appearance and the like of the obtained molded product are improved, but on the other hand, if it is too small, it becomes difficult to handle the master pelletized red phosphorus-based flame retardant, which is not preferable. . Commercial products of such microencapsulated red phosphorus include NOVA EXCEL 140 (trade name, manufactured by Rin Kagaku Kogyo Co., Ltd.), and Hishigard TP10 (trade name, Nippon Chemical Industry Co., Ltd.).

The thermoplastic resin substantially composed of an aromatic polycarbonate resin used in the master-pelletized red phosphorus-based flame retardant used in the present invention refers to at least 80% by weight in 100% by weight of the thermoplastic resin. %
And a thermoplastic resin composed of a thermoplastic resin other than the aromatic polycarbonate resin. As the aromatic polycarbonate resin, those described as the component a of the present invention can be used. As the thermoplastic resin other than the aromatic polycarbonate resin, those described as the component b of the present invention can be used. Particularly preferably, as in the case of the component b, an aromatic polyester such as polyalkylene terephthalate is used. Resin, vinyl-based thermoplastic resin.

Further, in producing such a master pelletized red phosphorus flame retardant, a phosphoric acid ester such as triphenyl phosphate or triphenyl phosphite, trisnonyl phenyl phosphite, Distearyl pentaerythritol diphosphite, bis (2,6-di-t
phosphites such as tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
The addition of 001 to 1% by weight is preferable because the thermal stability is improved.

A part or all of the aromatic polycarbonate resin of the component a constituting the flame-retardant resin molded product of the present invention is derived from the master-pelletized red phosphorus-based flame retardant used in the present invention. It will be. In the case where it is derived from a part, it suffices to satisfy the condition as the component a as a whole as a matter of course. Therefore, the aromatic polycarbonate resin derived from the master pelletized red phosphorus flame retardant may be different from the remaining aromatic polycarbonate resin. Similarly, for the other thermoplastic resin mixed in the master pelletized red phosphorus flame retardant, other thermoplastic resin derived from the master pelletized red phosphorus flame retardant and the remaining part The other thermoplastic resin may be different from the aromatic polycarbonate resin.

The master-pelletized red phosphorus-based flame retardant of the present invention comprises 80 to 95% by weight of a thermoplastic resin substantially consisting of an aromatic polycarbonate resin and 5 to 20% of red phosphorus.
% By weight and a specific surface area of 8 to 80 cm ² / g. A more preferred specific surface area is 9 to 2
5 cm ² / g.

When the content of red phosphorus is less than 5% by weight, the efficiency of imparting the flame retardant effect to the flame-retardant resin composition is poor, and when it exceeds 20% by weight, it belongs to the Class 2 dangerous substances under the Fire Services Act. , Not preferred in terms of safety. Here, when the test article ignites within 3 seconds and is determined to continue burning in the small gas flame ignition test, the case of belonging to the Fire Service Law Dangerous Goods Class 2 Class 1 Dangerous Goods Class 1 Those which are considered to be flammable solids and whose ignition time is within 3 to 10 seconds or which continue burning for 10 seconds or more after releasing the flame are treated as Class 2 flammable solids of the dangerous goods type 2. In addition, a fire extinguishing time exceeding 10 seconds or extinguishing within 10 seconds in such a test is a non-dangerous substance.

With respect to the specific surface area, if the specific surface area is less than 8 cm ² / g, it is not preferable because the pellets are large and biting defects occur during processing. If it exceeds 80 cm ² / g, the pellets may be dusted and the handling will be poor, and red phosphorus will be more likely to be present on the surface.

In the present invention, the specific surface area used for specifying the master-pelletized red phosphorus-based flame retardant is as follows:
From the uniformly mixed master pellets, 100 are randomly sampled, the surface area is calculated and the weight is measured for each pellet, and the average value is calculated.

Here, the surface area is calculated using a formula for determining the surface area by applying the shape of the pellet to a similar representative solid and measuring parameters required for calculating the surface area of the solid from the pellet. Is calculated. Such typical solids include a tetrahedron, a rectangular parallelepiped, a hexagonal prism, a cylinder, a hollow cylinder, a truncated cylinder, a truncated pyramid, a cone, a truncated cone, a pyramid, a cubic body, a ring, a sphere, a missing sphere, Spherical wedge type (see Handbook of Standard Mechanical Design Drawings, 2nd Edition). The necessary parameters, for example, in the case of a cylinder, correspond to the diameter and length of the pellet, and the amount is measured using a caliper or a micrometer.

The method for producing the aromatic polycarbonate resin pellets containing red phosphorus used in the present invention is described in detail in the above aromatic polycarbonate resin, red phosphorus,
More preferably, microencapsulated red phosphorus is preliminarily blended or independently supplied by a measuring device, and pelletized by a single screw extruder or a twin screw extruder. For example, using a twin-screw extruder, side-feed microencapsulated red phosphorus.
It is preferable to manufacture in a nitrogen atmosphere.

The flame-retardant resin molded product of the present invention comprises an aromatic polycarbonate resin (component (a)) and optionally the following components (b) to (d).
Thermoplastic resin composition (α component) containing components, ie, thermoplastic resin (b component) other than aromatic polycarbonate resin, reinforcing filler (c component), and flame retardant (d component) other than red phosphorus And red phosphorus (β component), 100% by weight of the resin composition, α component is 90 to 99.9% by weight, β component is 0.1 to 10% by weight, and It is based on a resin composition in which the component a is at least 10% by weight or more.

The components to be arbitrarily mixed need to be in an amount within a range in which the intended effects of each component can be sufficiently exerted upon mixing, and the resin composition constituting the flame-retardant resin molded product of the present invention is required. In 100% by weight of the product, the component b is 1-4.
0% by weight, 1 to 55% by weight for the component c, and 0.05 to 20% by weight for the component d. b component is 1
When the amount is less than 10% by weight, the impact resistance, chemical resistance, fluidity, appearance and the like obtained by mixing the component b are insufficiently improved. Strength cannot be maintained. c component is 1
If the amount is less than 55% by weight, the reinforcing effect is not sufficient, and if it exceeds 55% by weight, the moldability becomes poor. If the d component is less than 0.05% by weight, the expected flame retardant effect cannot be obtained, and if it exceeds 20% by weight, the mechanical strength of the flame-retardant resin molded product decreases.

Further, the flame-retardant resin molded product of the present invention preferably comprises 15 to 80% by weight of component a, 5 to 35% by weight of component b,
A resin composition comprising 10 to 45% by weight of component c, 0.05 to 15% by weight of component d, and 0.3 to 5% by weight of component β has strength, rigidity, impact resistance and dimensional stability. , Flame retardancy, fluidity, and the balance of each property of appearance,
It is more preferable to keep good.

The resin composition constituting the flame-retardant resin molded product of the present invention includes a phosphate ester such as trimethyl phosphate, or triphenyl phosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, Bis (2,6-di-tert
By further adding 0.005 to 1 part by weight of a phosphite such as (-butyl-4-methylphenyl) pentaerythritol diphosphite to 100 parts by weight of the resin composition, the thermal stability is further improved. Is preferred. Further, as long as the object of the present invention is not impaired, additives known as additives for various resins at present may be added.
In particular, it is preferable to use polytetrafluoroethylene having a fibril forming ability as an anti-drip agent, and such polytetrafluoroethylene is classified into Type III in the ASTM standard. Such polytetrafluoroethylene having a fibril-forming ability is commercially available, for example, as Teflon 6J from Mitsui-DuPont Fluorochemicals Co., Ltd. or as Polyflon from Daikin Industries, Ltd., and can be easily obtained. The amount of the anti-drip agent is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the resin composition constituting the flame-retardant resin molded product. 0.
If the amount is less than 01 parts by weight, the drip prevention effect is not sufficient, and 2
Exceeding the parts by weight adversely affects the appearance of the molded article. Other various additives include antioxidants such as hindered phenol compounds, antistatic agents, ultraviolet absorbers, release agents, slidability-imparting agents, flow modifiers, foaming agents, and especially represented by tetrazole compounds. And a coloring agent such as a pigment and a dye.

In order to produce the flame-retardant resin molded product of the present invention, a master pelletized red phosphorus used in blending the above-mentioned component a, and optionally components b to d, and red phosphorus as the β component. A flame retardant and, if necessary, other additives, preferably a tumbler, a V-type blender,
After uniform mixing by a mixer such as a Nauta mixer, the flame retardancy is achieved by applying to Banbury mixer, kneading roll, extruder, injection molding machine, compression molding machine, blow molding machine, vacuum molding machine, etc. A resin molding can be manufactured. In such a case, by using a master-pelletized red phosphorus-based flame retardant, it is possible to manufacture without using dangerous substances of the Fire Service Law. It is possible to manufacture with exactly the same equipment and working method. Even more preferably, after obtaining a flame-retardant resin molded product of the present invention in the form of a pellet, tube or sheet using an extrusion molding machine, an extrusion molding machine, an injection molding machine, a compression molding machine, a blow molding machine, And a method of obtaining a final flame-retardant resin molded product by applying to a vacuum molding machine or the like. The flame-retardant resin molded product thus obtained is excellent in flame retardancy and the like, and can be used for a wide range of applications such as electronic / electric and OA parts.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples. (1) Preparation of Master Pelletized Red Phosphorus Flame Retardant [Reference Example 1] (Production of Master 1) Aromatic polycarbonate resin (manufactured by Teijin Chemicals Limited, L-
1225WP, viscosity average molecular weight 2,500) 83.4.
8 parts by weight and 0.02 parts by weight of trimethyl phosphate were uniformly mixed using a V-type blender. Then, using a vented twin-screw extruder with a diameter of 30 mm [TEX30XSST manufactured by Nippon Steel Works, Ltd.], the mixture was microencapsulated from the first inlet at the end of red phosphorus [manufactured by Rin Chemical Industry Co., Ltd.] Nova Excel 140, content of red phosphorus 92% by weight, average particle diameter 35 μm] was measured from the second input port of the side feed portion in the middle of the cylinder using a measuring instrument [CWF manufactured by Kubota Corporation] using a mixture at the first input port. The microencapsulated red phosphorus in the second inlet was charged at 16.5 parts by weight with respect to 83.5 parts by weight. Each charging section was set to a nitrogen gas atmosphere with a nitrogen gas cylinder, the cylinder temperature was set to 280 ° C.
After using a material having holes, extruding strands and cooling with a cooling bath, pelletization was performed with a pelletizer. After uniformly mixing such pellets with a V-type blender,
Zero pellets were taken out, and the pellet was regarded as a cylinder. The diameter and length were measured with a digital caliper to calculate the surface area, and the weight was measured with an electronic balance to calculate the value of the specific surface area. Thereby, the red phosphorus content is 15% by weight, the specific surface area is 1%.
A 5.5 cm ² / g master pelletized red phosphorus-based flame retardant (Master 1) was obtained.

Reference Example 2 (Manufacture of Master 2) The same as Reference Example 1 except that the die was changed to one having 40 circular holes having a diameter of 0.5 mmφ and the pellet length was shortened by changing the pelletizer. Preparation and calculation of specific surface area were performed. Thus, a master-pelletized red phosphorus-based flame retardant (master 2) having a red phosphorus content of 15% by weight and a specific surface area of 85 cm ² / g was obtained.

Reference Example 3 (Manufacture of Master 3) The same as Reference Example 1 except that the die was changed to one having a circular hole having a diameter of 6.5 mmφ, and the pellet length was increased by adjusting the pelletizer. Preparation and calculation of specific surface area were performed. As a result, a master-pelletized red phosphorus-based flame retardant (master 3) having a red phosphorus content of 15% by weight and a specific surface area of 7.3 cm ² / g was obtained.

Reference Example 4 (Preparation of Master 4) Using 67.48 parts by weight of an aromatic polycarbonate resin and 0.02 parts by weight of trimethyl phosphate, 67.5 parts by weight of the mixture at the first inlet was used. Preparation and specific surface area were calculated in the same manner as in Reference Example 1 except that the microencapsulated red phosphorus in the two inlets was charged so as to be 32.5 parts by weight. Thereby, a master-pelletized red phosphorus-based flame retardant (master 4) having a red phosphorus content of 30% by weight and a specific surface area of 15.5 cm ² / g was obtained.

(2) Preparation of Flame-Retardant Resin Molded Products [Examples 1 to 6, Comparative Examples 1 to 5] The V-type blender was prepared by mixing the components shown in Tables 1 and 2 with the mixing ratios shown in Tables 1 and 2. After mixing (in the table, the composition ratio in the composition is shown for easy understanding), and a vent-type twin-screw extruder with a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works Ltd.] is used. Using a vacuum pump under a vacuum of 40 mmHg, cylinder temperature 25
Extrusion was performed at 0 to 260 ° C to obtain a pellet-shaped flame-retardant resin molded product. The pellets were dried using a hot air dryer at 110 ° C. for 5 hours, and then injected with an injection molding machine [T-150 manufactured by FANUC Corporation].
D], various test pieces were prepared at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C., and evaluated by the following methods.

(I) Mechanical properties of flame-retardant resin molded article Rigidity: Flexural modulus was measured according to ASTM D-790. Impact resistance: Izod notched impact was measured according to ASTM D-256. Heat resistance: 1 according to ASTM D-648
The deflection temperature under load was measured at a load of 8.6 kgf / cm ² . Flammability: A flammability test was performed according to UL Standard 94V.

(Ii) Productivity of Flame-Retardant Resin Molded Product Handling: Handling of Red Phosphorus-Based Flame Retardant Good; ×: Poor dust or poor biting during processing. Safety ○: Red phosphorus-based flame retardant does not belong to dangerous goods under the Fire Service Law. X: The red phosphorus-based flame retardant belongs to the dangerous fire class 2 of the Fire Service Law.

The symbols indicating the components shown in Tables 1 and 2 are as follows. Raw materials other than red phosphorus flame retardants (component a) PC: aromatic polycarbonate resin [Teijin Chemicals Co., Ltd.
ABS: Butadiene rubber reinforced acrylonitrile-styrene copolymer [ABS resin Santac UT-61, manufactured by Mitsui Toatsu Chemicals, Inc.] PEST: polyethylene terephthalate resin [B-12 component, viscosity average molecular weight 22,500] Teijin Ltd. TR-8580, intrinsic viscosity 0.8] Rubber-1: Butadiene rubber reinforced methyl methacrylate copolymer [Kureha Chemical Industry Co., Ltd. Paraloid EXL-26]
02] Rubber-2: Composite rubber-based graft copolymer [METABLEN S-2001 manufactured by Mitsubishi Rayon Co., Ltd.] (c component) Reinforcing filler-1: Talc [Talc P manufactured by Nippon Talc Co., Ltd.]
-3, average particle diameter of about 2.8 μm] Reinforcing filler-2: glass fiber [Nittobo Co., Ltd. 3PE-
941, fiber diameter 13 µm, cut length 6 mm] Reinforcing filler-3: glass powder [PFE-3 manufactured by Nittobo Co., Ltd.]
01, fiber diameter 9 μm, average fiber length 40 μm] Reinforcing filler-4: Mica powder [A, manufactured by Mika Yamaguchi Mfg. Co., Ltd.
-41, average particle size of 40 μm] (d component) Flame retardant-1: Halogen flame retardant (carbonate oligomer of tetrabromobisphenol A) [Teijin Chemical Co., Ltd.]
FG-7000] Flame retardant-2: Phosphorus flame retardant (triphenyl phosphate) [TPP manufactured by Daihachi Chemical Co., Ltd.] (Others) Additive-1: Distearylpentaerythritol diphosphite Additive-2: Trimethyl phosphate Anti-drip agent: Polytetrafluoroethylene having fibril-forming ability [Polyflon F manufactured by Daikin Industries, Ltd.]
-201L] Red phosphorus flame retardant Master 1: [Red phosphorus content: 15% by weight, specific surface area: 1]
5.5 cm ² / g] Master 2: [Red phosphorus content 15% by weight, specific surface area: 8
5 cm ² / g] Master 3: [Red phosphorus content 15% by weight, specific surface area:
7.3 cm ² / g] Master 4: [Red phosphorus content: 30% by weight, specific surface area: 1]
5.5 cm ² / g] Flame retardant-3: Red phosphorus-based flame retardant (microencapsulated red phosphorus) [Nova Excel 140 manufactured by Rin Kagaku Kogyo Co., Ltd.]

[0051]

[Table 1]

[0052]

[Table 2]

As is clear from the table, when Example 1 and Comparative Example 1 are compared, when the specific surface area of the master-pelletized red phosphorus-based flame retardant is larger than the range of the present invention, the work is caused by dust generation. It turns out that the property deteriorates. On the other hand, as can be seen from Comparative Example 2, when the specific surface area of the red phosphorus-based flame retardant is too small, poor entrapment occurs and workability deteriorates.

From the comparison between Example 1 and Comparative Example 3, when the red phosphorus concentration in the red phosphorus-based flame retardant is too high,
The safety of the work is insufficient because it is a dangerous substance. Further, in comparison with Comparative Example 4, the microencapsulated red phosphorus-based flame retardant is not only inferior in handling and safety but also in flame retardancy. It turns out that it is also inferior. Further, a comparison between Example 2 and Comparative Example 5 shows that the same behavior is obtained when the reinforced filler is used.

[0055]

The flame-retardant resin molded product of the present invention is extremely excellent in workability and safety in such production, and can be produced without using special equipment as in the case of ordinary resin molded products. Since it also has high flame retardancy, it can be used in a wide range of fields such as OA equipment and home electric appliances.

Claims (4)

[Claims] 1. An aromatic polycarbonate resin (component (a)), optionally the following components (b) to (d), that is, a thermoplastic resin (b) other than the aromatic polycarbonate resin, a reinforcing filler (component (c)), and In a resin composition comprising a thermoplastic resin composition (α component) containing a flame retardant other than red phosphorus (d component) and red phosphorus (β component), the α component is 90 to 90% by weight of the resin composition. 99.9% by weight, the β component is 0.1 to 10% by weight, and a
In the method for producing a flame-retardant resin molded product comprising a resin composition having a component content of at least 10% by weight or more, when the β component is blended, 80 to 95% by weight of a thermoplastic resin substantially consisting of an aromatic polycarbonate resin; Red phosphorus 5-20
A method for producing a flame-retardant resin molded product, comprising using a master-pelletized red phosphorus-based flame retardant having a specific surface area of 8 to 80 cm ² / g. 2. The master-pelletized red phosphorus-based flame retardant is manufactured using red phosphorus microencapsulated with a thermosetting resin and / or an inorganic material. 3. The method for producing a flame-retardant resin molded product according to 1.). 3. The composition according to claim 1, wherein each of the components is a to 15-80.
% By weight, 5 to 35% by weight of component b, 10 to 45% by weight of component c, 0.05 to 15% by weight of component d, and 0.3 to 0.3% of β component.
The method for producing a flame-retardant resin molded product according to any one of claims 1 and 2, which is a resin composition comprising 5% by weight. 4. The specific surface area of the master phosphorus pelletized red phosphorus flame retardant is 9 to 25 cm ² / g.
Item 14. The method for producing a flame-retardant resin molded product according to any one of Items 1.