TW200538502A - Halogen free ignition resistant thermoplastic resin compositions - Google Patents

Abstract

The present invention is a halogen-free ignition resistant polymer composition comprising: (A) a thermoplastic polymer or polymer blend, (B) a modified multi-functional epoxy resin containing from 0-20 wt. percent residual epoxy groups, based on the total weight of the epoxy resin, and (C) a phosphorus containing compound. The use of a modified multifunctional epoxy compound having from 0-20 weight percent residual epoxy groups, enhances the flame retardancy of the thermoplastic polymer, and can increase the compatibility of the epoxy resin with the thermoplastic polymer through the use of the modified functionalities, without causing black specks in the final product. It has been additionally discovered that modified multi-functional epoxy resins can also contribute to improved mechanical properties, melt flow rate and processability.

Description

200538502 发明 Description of the invention: [Technical Field of the Invention] The present invention relates to a thermoplastic polymer composition capable of exhibiting flame retardancy without using a halogen-containing compound. 5 [Prior art] Flame-retardant polymers typically use halogen-containing compounds to provide flame retardancy. However, the demand for halogen-free compositions has increased in the flame-retardant polymer market. Mixtures of polyphenylene ether resin and triphenylphosphine oxide have also been used as flame retardant components, as disclosed by Haaf et al. In U.S. Patent No. 4,107,232. However, these compositions have high viscosity due to the presence of high molecular weight polyphenylene ether resins, making them difficult to handle through extrusion or injection molding equipment.

It has been proposed to use phosphorus-based flame retardants instead of halogenated flame retardants in thermosetting epoxy resin compositions, for example, in EP A 0384939, EP A 15 0384940, EP A 0408990, DE A 4308184, DE A 4308185, DE A 4308187, WO A 96/07685, and WO A 96/07686. In these compositions, the phosphorus flame retardant is pre-treated with epoxy resin to form a bi- or polyfunctional soil milkweed 然后 and then an amine-based cross-linking agent (such as dicyanodiamide, sulfa, Or some other nitrogen-containing cross-linking agent) curing to form a network. 20 However, these compositions are thermosetting and cannot be used for injection molding applications. JP2001-49096 discloses a flame-retardant resin composition of a polyester resin, a stupid vinyl resin (for example, HIPS), and a flame retardant (for example, a dish-containing compound) combined with an aromatic epoxy resin. The jP2000-239543 case discloses a flame-retardant resin composition comprising a thermoplastic resin and a phosphorus-containing compound combined with a polyarylate or aromatic 200538502 aromatic epoxy resin. Polymer 43 (2002) 2249-2253, "Studies on the thermal stabilization enhancement of ABS; synergistic" effect by 5 triphenyl phosphate and epoxy resin mixtures), ABS composition containing various flame retardants of epoxy resin and triphenyl phosphate is investigated. However, 'the epoxy resin used in the above composition contains a high content of reactive epoxy groups' which reacts during the polymer treatment, causing black spots in the finished product. Therefore, there is still a need to provide a halogen-free thermoplastic polymer composition which can be used for injection molding applications, has good flame retardancy and heat resistance, which can overcome the shortcomings of conventional techniques. C Ming Nai ^^ The present invention relates to a halogen-free flame retardant thermoplastic polymer 15 composition, including: A) a thermoplastic polymer or polymer blend; and B) modified polyfunctional -Based epoxy resin, which contains a residual% of 0-20% by weight, oxygen based on the total weight of the epoxy resin; and C) a compound containing phosphorus. 20 Another embodiment of the present invention is a flame retardant polymer-grade product containing no element I, comprising: A) 40 to 94% by weight (based on the total weight of the composition) of a thermoplastic polymer Blended with 10-35% by weight (based on the total weight of the composition) of a polybenzyl scale polymer (such as polyphenylene oxide (PP0)), 200538502 b) 1 to 30% by weight (based on composition (Based on the total weight of the material) based on the modified yttrium% oxygen resin, which contains 0-20% by weight (based on the total weight of the epoxy resin) of residual epoxy groups; and C) 5 to 30% by weight Phosphorus compound (such as aryl phosphate) based on the total weight of the composition. The use of modified polyfunctional epoxides with 0-20% by weight of residual epoxy groups promotes the flame retardancy of thermoplastic polymers, and the use of modified B can increase the epoxy resin and thermoplastic polymers. Compatibility, and will not cause black spots in the final product. It has also been found that modified polyfunctional epoxy resins also contribute to improved mechanical properties, melt flow rates, and processing properties. Component (A) of the halogen-free flame-retardant polymer composition is a thermoplastic polymer or a polymer blend. Typical thermoplastic polymers include, without limitation, polymers made from vinyl aromatic monomers and their hydrogenated forms (including dienes and aromatic hydrogenated forms), such as styrene-butadiene fluorene copolymers, Polystyrene (including high-impact polystyrene), Acrylic acid_butadiene_styrene (ABS) copolymer, and styrene-acrylonitrile copolymer (SAN); Polycarbonate (PC), ABS / PC composition, polyethylene terephthalate, epoxy resin, hydroxyphenoxy ether polymer (PHE), such as taught by U.S. Patent Nos. 20,275,853; 5,496,910; 3,305,528, vinyl alcohol Copolymers, ethylene acrylic acid copolymers, paraffin carbon monoxide heteropolymers, polyolefins, cyclic olefin copolymers (COC), copolymers of other olefins (especially polyethylene copolymers), and homopolymers (such as , Using traditional heterogeneous catalysts), polyphenylene ether polymer (PPO) and any mixtures thereof or 200538502 compounds. Thermoplastic polymers and methods of manufacture are known to those skilled in the art. In one embodiment, the thermoplastic polymer is a rubber-modified monovinylidene aromatic polymer, which is prepared by polymerizing a 5 vinyl aromatic monomer due to the presence of a dissolved elastomer or rubber. Vinyl aromatic monomers include, without limitation, those described in U.S. Patent Nos. 4,666,987, 4,572,819, and 4,585,825. Preferably, the single system has the following chemical formula: wherein R is hydrogen or methyl, and Ar is an aromatic ring structure having 1 to 3 aromatic rings with or without alkyl, halo or i alkyl substitution. Wherein any 15 alkyl group contains 1 to 6 carbon atoms, and the i alkyl group refers to an alkyl group substituted with an i group. Preferably, Ar is phenyl or alkylphenyl, of which alkylphenyl means phenyl substituted with alkyl, and phenyl is most preferred. Typical vinyl aromatic monomers that can be used include: all isomers of styrene, methylstyrene, ethyltoluene, especially p-toluene, ethylstyrene, propyl 20 styrene All isomers of dilute, vinylbiben, vinylnaphthalene, vinylanthracene, and the like. Vinyl aromatic monomers can also be mixed with other copolymerizable monomers. Examples of such monomers include without limitation acrylic monomers, such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, acrylic acid, and methyl acetate; maleic acid Imine, phenylmaleimide, 25 and maleic anhydride. Rubber used to make rubber modified monovinylidene aromatic polymers 200538502 Any rubber that can promote the impact properties of monovinylidene aromatic polymers, including any molecular structure, such as linear, branched, star Branching, 5 10 15 and iso- and co-polymer diene rubber, block rubber, functional rubber 'low-cis, cis-cis rubber, and mixtures thereof. The preferred elastomer or rubber system exhibits a temperature of no less than 0 ° C, preferably no higher than 20 ° C, and more preferably no higher than 40 ° C. The second-stage transition temperature (determined using traditional techniques Or estimate, for example, polymers and copolymers of ASTM Test Method 52 τ). Rubber is typically formulated so that the rubber-reinforced polymer product contains 3 (preferred system 4, more preferred system 5, and optimal system 6) to 20 (preferred system cut, better system support, and optimal system). 14) The weight of "% of rubber (which is based on the total amount of vinyl aromatic monomers and rubber components of 4 as silk, used as the amount of rubber Nucor's spicy." Rubber "or" rubber equivalent "here When used, it means that for rubber homopolymers, such as' polymerized H is simply the amount of rubber, and for funnel copolymers, it is a copolymer consisting of monomers that form rubber polymers when homopolymerized. 'Such as' For succinic styrene copolymer, the amount of succinic component of the desired copolymer. Oak Rubber is present as individual rubber particles in the monovinylidene aromatic polymer matrix' And it can have any type, including unimodal, bimodal or multimodal particle ruler cloth and particle size, and any type, including porous, core-shell, and sheep skin, and any mixture of them. Vinyl aromatic monomers ▼ Renxi take people flat shares ♦ mouth hydration reaction methods and processing conditions, which are based on The rubber-refined gatherer's leftovers, the raw clothing, and the conditions required to make the desired average particle size are known to those skilled in the art.…, Know to those skilled in the art. Although any polymerization reaction Methods can be used, typical methods are continuous bulk or solution polymerization 20 200538502 reaction, as described in US-A-2,727,884 and US-A-3,639,372. The polymerization of vinyl aromatic monomers is based on pre-dissolved elastomers Existence is carried out to produce impact-modified, or grafted rubber-containing products, examples of which are described in US-A-3,123,655, US-A-3,346,520, US-A-3,639,522, and 5 US-A- No. 4,409,369. The rubber is typically a butadiene or isoprene rubber, preferably polybutadiene. Preferably, the rubber-modified vinyl aromatic polymer is a high impact polystyrene ( (HIPS) or acrylonitrile-butadiene-benzyl ethylene (ABS), and HIPS is the best. The thermoplastic polymer or polymer blend (A) is at least 40 parts by weight 10. (preferably at least 50 parts by weight ., Preferably at least 55 parts by weight, more preferably at least 60 parts by weight, and most preferably at least 65 parts by weight, based on 100 parts by weight The amount of the invention-free flame retardant polymer composition based on Li) is used in the present invention as the content of I-free flame retardant polymer composition. Generally, the thermoplastic polymer component (A) is based on It is used in an amount of less than or equal to 94 parts by weight (preferably less than or equal to 15 to 80 parts by weight based on 100 parts by weight of the halogen-free flame-retardant polymer composition of the present invention). In one embodiment, the composition of the present invention comprises a thermoplastic polymer and a thermoplastic blend of another thermoplastic polymer such as polyphenylene ether. Polyphenylene ether is self-catalyzed by various catalyzed and uncatalyzed methods Corresponding to 20 phenol or its reactive derivative. For example, certain polyphenylene ethers are disclosed in U.S. Patent Nos. 3,306,874 and 3,306,875, and U.S. Patent Nos. 3,257,357 and 3,257,358 to Stamatoff. In Hay's patent, polyphenylene ether is produced by an oxidative coupling reaction comprising a reaction solution containing a phenol and a metal-amine complex catalyst. Other disclosures of methods for making poly 10 200538502 polyphenylene ether resins (including graft copolymers of polyphenylene ether and styrenic compounds) are found in US Patent No. 3,356,761 to Fox; US Patent No. 3 to Sumitomo No. 1,291,609; U.S. Patent No. 3,337,499 to Bussink et al .; U.S. Patent No. 5 3,219,626 to Blanchard et al .; U.S. Patent No. 3,342,892 to Laakso et al .;

Borman U.S. Patent No. 3,344,166; Hod et al. U.S. Patent No. 3,384,619; Faurote et al. U.S. Patent No. 3,440,217; and disclosures on metal-based catalysts (which do not contain amines) The content can be known from patents such as U.S. Patent No. 3,442,885 (copper " 铜) by Wieden et al .; U.S. Patent No. 3,5? 3,257 (metal alkoxide) by Nakashio et al. Or salt); Kobayashi et al. US Patent No. 3,455,880 (Ming Chelate). In the patent of Stamatoff, polyphenylene ethers are based on the presence of corresponding phenate ions and initiators (such as peroxyacids, acid peroxides, and hypoacids) in the presence of a complexing agent. 15 was obtained by the reaction. Disclosures related to non-catalytic methods (such as oxidation reactions with heterodioxide, silver oxide, etc.) are described in US Patent No. 3,382,212 to% Price et al. U.S. Patent No. 3,383,435 to Cizek et al. Discloses a polystyrene bond. A styrene resin composition. The polyphenylene ether resin preferably has the following repeating structural chemical formula: 11 200538502

Among them, one unit of the oxygen ether atom is connected to the benzene nucleus of the next adjacent unit, n is a positive integer and is at least 50, and each (^ is selected from hydrogen, halogen, a hydrocarbon group without a third-order "carbon atom, A monovalent substituent of a group consisting of a halohydrocarbyl group having at least two carbon atoms, a alkoxy group, and a _alkoxy group having at least two carbon atoms between a halogen atom and a phenyl core. A preferred polyphenylene ether resin system Poly (2,6-difluorenyl-1,4-benzylidene) ether resin. When used in combination with another thermoplastic polymer, the polyphenylene ether resin is preferably at least 10 parts by weight (preferably at least 12 parts by weight, more preferably at least 15 10 parts by weight, and most preferably at least 18 parts by weight) and up to 35 parts by weight (preferably up to 30 parts by weight, more preferably up to 28 parts by weight, more preferably It is up to 25 parts by weight, which is based on 100 parts by weight of the non-flammable flame-retardant polymer composition of the present invention as a basis) for the non-flammable flame-retardant property of the present invention. Polymer composition. Polymers of thermoplastics and polyphenylene ethers can be manufactured from blends before being incorporated into the composition of the present invention, or A polymer can be incorporated individually. The component in the II-free flame-retardant polymer composition of the present invention is a modified polyfunctional epoxy resin. A modified polyfunctional epoxy resin It is an epoxy resin with at least two epoxy groups at the beginning, which has been reacted with at least one 12 200538502 compound capable of reacting with epoxy groups (hereinafter referred to as modifiers). Thus, the number of starting epoxy groups Is reduced and replaced with the functionality of the modifier compound. The modifier may also be selected to increase the compatibility of the modified multifunctional epoxy resin with a thermoplastic polymer or blend. Functional epoxy resins are known to be derived from non-halogenated polyfunctional epoxy resins, or polyfunctional epoxy resins which are substantially halogen-free. Resin is completely non-functional, that is, 0% free base, or the resin contains some trace ages that are not compatible with the properties or properties of the resin and are not detrimental to the resin: 10 Some polyfunctional epoxy resins can have very small Amount of homemade oxygen _2 ^ element impurity °-Hang 'used in the present invention Ring = 糸 start (before reacting with modifier compounds) per molecule at 1 (preferably at least J 8, oxime K K W, and most preferably 3) ring lice-based materials Section. The product formed after the modifier compound was washed (the modified multi-state oxyresin reaction jacket of __, ^ ;: = 舞 ^ contains 从 从 2, and better # 3 5ί 〇 (General Department It is preferably less than 15, preferably less than 12, and w soil from 10 to 10% by weight of the residual, moreover the total amount of oxygen resin is more than 20 based on the modified base. The wall can be any compound of saturated or unrefined aliphatic polyglycemic epoxy tree, love # 自 ^ 衣 月 日 无, aromatic or heterocyclic. Epoxy resin with ~~ U epoxy groups "Yan Ke Yi" materials include the epoxy epoxy novolac resins of the present invention group (such as ^ s month month sex lice resin 439, which is a quotation of the Dow Chemical Company, ϋ · Ε · Ν · Τ 43δ ^ · Ε · Ν, °. Name and can be purchased from it); Dicyclopentan 13 200538502 Dienol epoxy novolac resin; Epoxidized bisphenol-A novolac tree purpose, epoxidized cresol novolac resin, or in US 5,405,931 US 6,291,627 and US 6,486,242 and others found in WO 99/00451; 5 Epoxy novolac resin (sometimes called epoxidized novolac resin, used to include the term epoxy phenol novolac resin and epoxy formaldehyde novolac resin) has the following general chemical structure and chemical formula:

R R

Where "" R "is hydrogen, Q-C3 alkyl, or Q-C3 alkyl, for example, methyl 10; and" Π "is an integer of 0 or 1 to 10. '' "Preferably has an average value of 0 to 5.

Polyfunctional epoxy resins are readily available, for example, under the trade names D.E.N. (trademark of The Dow Chemical Company), and QuatrexTM, and triepoxides such as Tactix ™ 742 (trademark of Ciba). Commercial products generally include mixtures of various species of the above chemical formula, and a convenient way to describe the characteristics of such mixtures is the average value of n, n, for various species. The preferred multifunctional epoxy resin epoxy novolac resin, epoxycresol novolac resin, and epoxidized bisphenol A novolac resin used in accordance with the present invention, in which N has a value of 2.05 to 10, more preferably 2.5 to 5. Epoxidized bisphenol A novolac resin contains a polymer 20 having the following structure, of which GLY is a glycidyl group: 14 200538502

The tri-epoxy resin contains a polymer having the following structure:

Typically, the weight average molecular weight (Mw) of the polyfunctional epoxy resin depends on the thermoplastic polymer used in the composition of the present invention, and is generally from 150 (preferably from 250, more preferably from 350, and The optimal range is from 450) to! _00,000 (typically up to 50,000, typically up to 25,000, preferably up to 10 8,000, and more preferably up to 5,000) atomic mass units (amu). Modifiers for improving polyfunctional epoxy resins are compounds containing a reactive group that reacts with the oxygen functionality of the ring 15 200538502, such as a phosphonate group, for example, a compound such as 2-phenylphenol , 4-phenyl age, dimethylbenzene, tertiary butylphenol, bisphenol-a, bisphenol-f, polyisocyanates such as fluorenyl diphenyl diisocyanate and toluene diisocyanate, acid groups, acids Compounds, such as' salicylic acid 'amine groups, such as' continuous amines; acid if groups, such as horn anhydride, dodecyl succinic anhydride; or with halogen-free polyfunctional epoxy compounds Any scale-free group of epoxy groups. Other modifiers include compounds containing functionalities that promote the mechanical properties of the composition and are compatible with the thermoplastic resin. . For thermoplastic resins, such as monoethylene and 10-based aromatic compounds and co-consumed dilutes, these functionalities may include butadiene, styrene-maleic anhydride, polyisocyanates such as methylenedidiol, without limitation Benzyl diisocyanate and toluene diisocyanate, polybutadiene-maleic anhydride copolymer, butadiene terminated with carboxylic acid, and polystyrene functionalized with carboxylic acid. Any combination of modifiers can be used to improve polyfunctional epoxy resins. The modifier compound may contain, on average, one or more functionalities capable of reacting with epoxy groups per molecule. The modifier compound preferably contains an average of 0.8 to 5 (more preferably 0.9 to 4, and most preferably 1 to 3) functional groups capable of reacting with epoxy resin per molecule. 20 Modified polyfunctional epoxy resins can generally be made by any method ', but are typically known in the art by using polyfunctional epoxy resins and modifiers on catalysts (amines, acids, Gadolinium or ammonium catalyst) is obtained by heating above 80 ° C. The amount of the modified polyfunctional epoxy resin in the non-flammable flame-retardant polymer composition of the present invention 16 200538502 depends on the thermoplastic polymer used in the composition, and is typically at least 1 At least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, and most preferably at least 20% by weight and less than 30% by weight, preferably less than 28% % By weight, more preferably less than 5% by weight, and most preferably less than 20% by weight, based on the total weight of the halogen-free flame-retardant polymer composition. Compounds containing a phosphorus element may also be included in the composition of the present invention. These compounds may be non-epoxy-containing phosphorus-containing compounds. Appropriate 10 phosphorus compound-based organic phosphorus compounds as component (C) in the non-flammable flame-retardant polymer composition used in the present invention, which include organic phosphates, organic phosphites, and organic phosphonates , Organic linoleate, organic phosphinate, organic hypophosphonate, other androgen-containing compounds, such as 9,10-dihydro-9-. Ox, 10-phenanthrene-10-oxide (DOP); 10- (2,, 5, -dienylphenyl) -9,10-dihydro-9-ox-10-phenanthroline] oxide (D〇P-HQ); bis (4-hydroxyphenyl) -phosphine oxide, bis (2, hydroxyphenyl) phosphine oxide; dimethyl-1-bis (4-hydroxyphenyl) -1- Phenylmethylphosphonate; tris (2-hydroxy4 / 5-methylbenzyl) phosphine oxide; tris (4-hydroxy = yl) phosphine oxide; bis (2-hydroxyphenyl) phenylphosphine oxide; bis ( 2-hydroxyphenyl) benzyl-human acid, tris (2-side methylbenzyl) oxide; or a mixture thereof, which is further described below. The organic and compound systems of ITO are disclosed in, for example, U.S. Patent Nos. ^^ '' 2'645, and 5,276,007. The preferred organic phosphorus compound is a mono-weil compound represented by Chemical Formula I: 25 〇

p II i '(〇) mrP- (〇) m3-R3 (丨) 200538502

(〇) m2 I R2 wherein each of R !, R2, and R3 represents an aryl group and an alkaryl group, which are individually selected from each other, and each of rih, m2, and m3 is independently 0 or 1 from each other . The best monobasic compounds are monobasic acid esters, among which nh, m2, and m3 are all 1, and Ri, 112, and 113 are each methyl, phenyl, tolyl, xylyl, 10-cumyl, Naphthyl, for example, all isomers of trimethyl salt, triphenyl salt, tricresyl phosphate, and mixtures thereof, especially tris (4-methylphenyl) phosphate, All isomers of tris (xylyl) phosphate, and mixtures thereof, especially tris (2,6-dimethylphenyl) phosphate, tricresylcarboxylic acid, tricumyl filling acid g. all isomers, and mixtures thereof, 15 and trinaphthyl phthalates, or mixtures thereof. Another preferred organic phosphorus compound is a polyphosphorus compound represented by Chemical Formula II: 0 0

II II 20 R1- (0) m1-P-0-(-X-0-P- (0) m4-) n-R4

(II) I I (O) m2 (O) m3

II R2 R3 25 Among them, 1 ^, 112, 113, and 114 each represent an aryl group or an alkaryl group, which are individually selected from each other, and X is an aryl group derived from a dibasic compound, mb m2, m3 , And m4 are each independently 0 or 1, and when η is equal to or greater than 1, η has a value greater than 0 and less than 10 on average. Polyphosphorus compounds are sometimes referred to as oligomeric compounds. Preferred multi-walled compounds are polymorphic acid esters, among which, 200538502 m4 is 1, Rb r2, &, and 仏 is methyl, benzyl, tolyl, xylyl, bracket, naphthyl, and X. An arylene group derived from a dihydroxy compound, such as resorcinol, hydroquinone, double age A, and η has an average value greater than 0 and less than 5, preferably, η has an average value greater than 1 and less than 5 value. For example, compared with 5 ·, oligomeric scale esters having an η value between 1 and 2 are m-phenylene-bis (diphenyl 41¾), p-benzylidene-bis (diphenyl diacetate) , M-phenylene-bis (xylyl phosphate), p-phenylene-bis (xylyl phosphate), m-phenylene_bis (bis (dimethylbenzyl) acetic acid vinegar) , P-phenylene-bis (bis (xylyl) stele vinegar), bisphenol-A-bis (diphenyl phosphate), bisphenol A-bis (xylyl 10 phosphate), bis Phenol A-bis (bis (xylyl) phosphate), or a mixture thereof. Stone 4 compound component (c) is at least 5 (preferably at least 7, and more preferably, to)% by weight (which is 100 parts by weight of the halogen-free flame-retardant polymer composition of the present invention). As the benchmark), and up to 30 (preferably up to 15 27, more up to 25, more up to 23, and more up to 20) reset% (which is based on The total amount of the flame retardant polymer composition containing the functional element is based on the total weight of the flame retardant polymer composition used in the present invention. In addition, the halogen-free flame-retardant polymer composition may optionally contain one or more additives commonly used in this type of polymer composition. Preferred additives of this type include without limitation: antioxidants, impact modifiers such as styrene-butadiene rubber; plasticizers such as mineral oil; antistatic agents; flow promoters; release agents; Colorants; Wetting agents; Fluorescent additives; Fillers, such as calcium carbonate, calcium hydroxide, magnesium hydroxide, talc, clay, 19 200538502 mother, stone ash limestone, sintered glass beads, osmium oxide, evening stone, carbon Black, glass fiber, potassium titanate, single-layer ion exchange screens to replace prostitutes «materials or mixtures thereof» and perfluorocarbon oligomers and polymers (such as, polytetrafluoroethylene), its 5 15 series Physical and chemical foaming agent (including carbon dioxide) used to improve UL 94 droplets. Furthermore, the _, _ compound composition is stabilized against degradation caused by heat, light, and oxygen, or a mixture thereof (but not limited thereto).

Additives of the "amount of" element can be used, but preferably the composition is free of element, wherein the composition does not contain any halogen above 0.1% by weight (which is based on the total weight of the composition) If used, the amount of these additives will change and need to be controlled according to the specific end use, which can be easily and appropriately implemented by those skilled in the art.

In one embodiment, the composition of the present invention can be used for manufacturing a foam. The halogen-free flame-retardant polymer composition is spread to form a foamable mixture by melt processing with a foaming agent, and the foamable mixture is extruded through a mold to a reduced pressure region, and The foaming mixture expands and cools. Conventional foam extrusion equipment such as a screw extruder, a twin screw extruder, and a cumulative extrusion device can be used. A suitable method for making extruded foam from a resin / foaming agent mixture is described in U.S. Patent Nos. 2,409,910; 2,515,250; 2,669,751; 2,848,428; 2,928,130; 3,121,130; 20 3,121,911 3,770,688; 3,815,674; 3,960,792; 3,966,381; 4,085,073; 4,146,563; 4,229,396; 4,302,910; 4,421,866; 4,438,224; 4,454,086 and 4,486,550. The blowing agent is preferably a halogen-free blowing agent of a physical or chemical formula, and may be incorporated or mixed into the polymer material by any convenient means. The most typical 20 200538502, the physical foaming agent is fed into the sleeve of the extruder under pressure, during which the polymer is mixed. However, such mixing can be accomplished by various other means including a so-called static mixer or interface surface generator, such as described in Wu Guo Patent Nos. 3,751,377 and 3,817,669. Chemical clams can be mixed with the polymer beforehand or fed into the extruder with the polymer. The polymer / foaming agent mixture is then heated to a high pressure under sufficient pressure to expand the formed foamable mixture through an extrusion die; the Foten temperature (in physical foaming) In the case of chemical agents) or decomposition (in the case of chemical blowing agents) temperature. Typically, the foamable mixture is cooled to the foaming temperature in other mixing devices of the extruder 10 or in individual heat exchangers. The optimal foaming temperature at a 70% slope has the desired density and the desired cell size. Foam. Then, the foamable mixture enters the decompression and temperature reduction region through the mold, during which the 'foam expands and cools to form a cell structure. Foams can be extruded into any of a variety of different shapes, but are most commonly extruded to form a sheet (nominal thickness of 13 mm or less) or a plate (nominal thickness exceeding 13 mm). Sheet products are conveniently prepared using round molds. A tubular foam was produced, which was cut to form a flat sheet. Plate-shaped products are conveniently made using rectangular or "dog-bone" molds. Suitable physical blowing agents include carbon dioxide, nitrogen, lower alcohols, 20-alkyl ethers, water, and / or hydrocarbons, especially those with up to 6 atom breaks. Hydrocarbon blowing agents include pinane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclohexane and cyclopentane. Alcohols include methanol, ethanol, n-propanol, and isopropanol. Suitable alkyl ethers include dimethyl ether, diethyl ether and fluorenyl ethyl ether. Mixtures of two or more of these physical blowing agents 21 200538502 may be used. Suitable chemical foaming agents include azobiscarbon donkey amine, azobisisobutyronitrile, benzodiazide-hydrazine, 4,4-oxobenzothanthrene semi-carbaphe, p-toluene -Carbahydrazine, barium azodicarboxylate, N, Nf-dimethyl-N, Nf-dinitroso5 p-xylylenediamine, trishydrazinetriqin and sodium bicarbonate. Although the present invention relates to a halogen-free flame-retardant composition ', it should be noted that the halogenated foaming powder may be suitably implemented to generate a foam. However, preferably, an unhalogenated blowing agent is used. In one embodiment, a blowing agent containing a non-halogenated blowing agent mixture of lower alcohols having 1 to 4 carbon atoms, alkyl 10 ethers, alkyl esters, hydrocarbons, water (up to 50%) and carbon dioxide The mixture was used. Various auxiliary materials can be used in the foaming method. These auxiliary materials generally include cell control agents (nucleating agents), cell expansion agents, stability control agents (penetration modifiers), antistatic agents, cross-linking agents, processing aids (such as sliding agent 15) ), Stabilizers, flame retardants, UV absorbers, acid scavengers, dispersion aids, extrusion aids, antioxidants, colorants, and inorganic fillers. Cell control agents and stability control agents are used. Chevron Cell Control contains finely cut inorganic substances such as calcium carbonate, calcium silicate, indigo, talc, clay, titanium dioxide, silica, 20 calcium stearate, or diatomaceous earth, with a small amount of energy Chemicals that react to form gases under extrusion conditions, such as' citric acid or sodium citrate and undulated sodium bicarbonate. The amount of the nucleating agent used may range from 0.001 to 5 parts by weight per 100 parts by weight of the polymer resin system. A preferred range is 01 to 3 parts by weight. When a foaming agent is used as a marginal heating agent, additives that attenuate the infrared transmission through the foam structure may be incorporated to increase the insulating properties, even when the foaming agent contains an insulating gas. Examples of the infrared attenuating agent include a carbon black material, graphite, titanium dioxide, and aluminum particles. When an infrared attenuator is used, a reduced proportion of the insulating foaming agent can be used. 5 If desired, the foaming agent may undergo various subsequent processing steps. Generally, it is desired to cure the foam (ie, to replace the foaming agent in the cells with air). The processing step to reduce the curing time includes perforation, as described in U.S. Patent No. 5,424,016, to heat the foam at a slightly elevated (io_13_00f) temperature for several days to weeks, or Their combination. In addition, the foam can be pulverized to open the cells. A crosslinking step can also be performed. The production of the flame retardant polymer composition free of vitamins in the present invention can be accomplished by appropriate mixing means known in the art, including dry blending of individual components and subsequent melt mixing, which can be used in The extruder used to make the finished item is either directly in the extruder or pre-mixed in the individual extruder. The 15 dry blends of the composition can also be directly injection molded without mixing. The flame retardant polymer composition containing no tooth element of the present invention, and the polymer-based thermoplastic polymer contained in 1. When softened or smelted by applying heat, the non-flammable flame-retardant polymer composition of the present invention can be formed or molded using conventional techniques such as compression molding, injection molding, and gas-assisted injection. Forming, calendering, vacuum forming, thermoforming, extrusion and / or blow molding can be used alone or in combination. j The flame retardant polymer composition of 3 leucoline can also be formed, spun, or stretched into a sheet of extruded 溥%, fiber, or multilayer laminate, or it can be grown with Organic or inorganic substances are combined on any machine suitable for this purpose. 23 200538502 In one embodiment, the present invention is a halogen-free flame-retardant polymer composition, which basically consists of the following: A) a thermoplastic polymer or polymer blend, B) modified Multifunctional epoxy resin, containing 0-20% by weight of 5 residual epoxy groups, which is based on the total weight of the epoxy resin, and C) a compound containing a dish. In another embodiment, the present invention is a halogen-free flame-retardant polymer composition, which basically consists of the following: A) 40-94% by weight, based on the total weight of the composition, thermoplastic 10-based polymer, which may optionally contain 10-35% by weight, based on the total weight of the composition, a polyphenylene ether polymer, such as polyphenylene oxide (PPO), B) 1- 30% by weight, based on the total weight of the composition, the modified polyfunctional epoxy resin contains 0-20% by weight of residual epoxy groups, and 15 is based on the total weight of the epoxy resin , And C) 5-30% by weight, based on the total weight of the composition, a phosphorus compound, such as an aryl acid, is intended. The term "consisting essentially of" means that the listed components are essential, even though other materials may be present in small amounts without significantly altering the nature or purpose of the composition of the invention. Preferably, the composition of the present invention does not contain a thermosetting polymer. The halogen-free flame-retardant polymer composition of the present invention is used for manufacturing various useful objects and parts. Some items that are particularly suitable include TV cases, computer screens, and related printer cases that typically require excellent combustion classification. Other applications include automobiles and gadgets. 200538502 [Embodiment] The following implementation examples are examples of the present invention. These examples are not intended to limit the scope of the invention, and they should not be construed as such. Contents are, inter alia, parts or percentages by weight. 5 Combustion classification is obtained by testing under UL-94 vertical (V) or UL-94 horizontal (HB) flammability tests. For the vertical combustion test, five test specimens of a desired thickness measuring 12.5 mm (mm) x 125 mm suspended vertically on surgical cotton were burned with a 1875111111 Bunsen burner flame; the sample was subjected to secondary combustion (10 seconds each time). The grading criteria include the total embers time of 10 after each ignition, the growth time after the second ignition, and whether the bar drips the flame particles that ignite the cotton. Melt flow rate is determined according to ASTM D1238. Cantilever beam is determined according to ASTM D256. Tensile resistance is determined according to ASTM D638. 15 Elongation is determined according to ASTM D638. Vicat is determined according to ASTM D1525. Resin manufacturing process The modified epoxy novolac resin is manufactured in a 10-liter steel reactor (which is equipped with a mechanical stirrer, a heating jacket, an N2 inlet and a condenser). DEN 438 (Dow's epoxy novolac) (57% by weight) and 2-phenylphenol (43% by weight) were contacted at a temperature between 125 and 185 ° C. About 20-30% of the water is injected into the reactor with epoxy linear water and heated to 110 ° C. About 1,000 ppm of triphenylethyl squamyl acetate catalyst (based on total solids) was added to the resin and heated up to 130 ° C. The remaining modifiers were added to the reaction mixture in portions. In this way, the temperature of the reaction mixture can be controlled at 185 ° C. After all the modifier compounds were added, the temperature of the reaction mixture was maintained at 175 ° C for about 30 minutes, and the product was tabletted into a solid. The final product has an epoxy content of 2.83%, a melt viscosity of 0.20 to 3 ^ 5 (at 150 ° C) and a resin Tg of 45/43 ° C. High-impact polystyrene (HIPS, Mw 185,000, rubber content 10.5% 'unimodal distribution (average 2 microns), ο' wt% mineral oil), polyphenylene oxide and modified epoxy novolac ( Manufactured as above, the composition of DEN / OPP) is molded by injection molding after melting and melting. The product was compounded on a Wernej phieiderer 30 10 mm twin-screw extruder (which has a zone temperature of 125, 18, 245, 25 ° & 26 ° ...). The samples were injection molded on DeMag injection molding machines (226, 226, 230, and 23 (area temperature of TC)), and the mold temperature was 54 °.

26 200538502 Comparative Example Throughout Example I Weight% of Comparative Example HIPS 60 55 55 55 Weight% of PPO 22 22 22 22 Weight% of FP-500 18 18 18 18 Weight% of epoxy 0 5 5 5 Epoxy— DEN / OP Novolac epoxy novolac P aldehyde melt flow rate (g / 10 3.8 5.6 44 4.2 minutes) Cantilever (sigh • broken / inch size) 2.2 1.7 1.4 1.2 (J / m) 115 90 75 65 Tensile Yield (psi) 5878 4245 5560 5790 (MPa) 40 29 38 40 Elongation 8 19 11 4 Vicat (° c) 96 93 103 93 Flame drip 5/5 0/10 0/10 0/10 UL classification 2.5 mm V-2 V-0 V-0 V-0 DEN = Dow ’s Epoxy Novolac 438 OPP is 2-phenylphenol FP-500 is available from Daihachi Chemical It is a product of Bakelite, and the product number is 〇79〇κ〇3. Epoxy novolac is a polyfunctional epoxy novolac having a functional average of 5.5 and an epoxy equivalent of ΐ87. Further compositions can generally be manufactured similarly as described above to provide compositions reviewed and evaluated in the table using the following test methods. • Melt flow rate (MFR) is determined in accordance with ISO 1183. 10 Cantilever beam system is determined according to ISO 180. 200538502 The tensile yield (Ty), tensile modulus and elongation are determined according to ISO 527. The heat torsion temperature (HDT) is determined in accordance with ISO 75 under conditions of 1 · 8 Mpa and 12.0X over 1 hour. In these experiments, the PPO component used was Asahi N-2245 brand 5 resin, which is a blend of about 70% polyphenylene oxide polymer (PP0) and about 30% polystyrene and rubber. (It is considered a part of the overall HIPS component in the table below). The HIPS Feedstock resins referred to in the table below are high-impact polystyrene resins as described and used in the examples above. Among these compositions, the phosphorus-containing compounds are BAPP (which is bisphenol A bis (diphenylphosphonate)) and RDP (which is tolylene bisphenol bis (diphenyl phosphate)). The modified epoxy resin is a modified epoxy novolac resin prepared as described in the above experiment, and is a reaction product of o-phenylphenol and Dow's epoxy novolac (DEN 438). The results shown in the following sample compositions 7 and 8 are based on the composition and property simulation techniques of those skilled in the art.

28 200538502 Sample composition 2 3 4 5 6 7 8% by weight of HIPS Feedstock 40.8 39.6 43 36.8 31 o 〇〇JD.D 19.3% by weight of HIPS * 51.9 49.6 53 47.8 44 43.3 34.3% by weight of Asahi N-2245 37.1 34.3 32.9 37.1 42.9 38.6 48.6% by weight of PP0 26.0 24.0 23.0 26.0 30.0 28.0 34.0% by weight of modified epoxy novolac resin 5 5 5 5 5 5 5 Polyphosphate RDP BAPP BAPP BAPP BAPP BAPP BAPP BAPP Phosphate % 17 21 19 21 21 23 27% of Teflon 6-CN 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sample properties MFR (g / 10 min) 9.3 11.2 10 9.9 9.0 9 5.0 Cantilever beam (J / m) 103 81 80 80 70 65 50 Ty (MPa) 38.5 43.8 40 45.1 48.7 46 50 Elongation (%) 55 49 50 42 32 25 15 Modulus (MPa) 2271 2500 2450 2520 2580 2550 2650 HDT (° C) 59.7 61.5 62 61.5 64.2 62 67 Sp Dens (kg / 1) 1.112 1.112 1.114 1.113 1.115 1.124 1.132 UL V-94 combustion classification (3.0 mm) VI VI VI VO VO VO VO The total HIPS component contains polystyrene and rubber contained in Asahi N-2245 Of its blend. 200538502 i: Brief description of the drawing 3 (None) [The main component representative symbol table of ._ type] (None)

30

Claims (1)

200538502 Scope of patent application ... 1. A halogen-free flame retardant polymer composition, including ... A) thermoplastic polymer or polymer blend; The mounting epoxy resin contains 5% by weight of a residual epoxy group, which is based on the total weight of the epoxy resin, and C) a compound containing a dish. 2. A halogen-free polymer composition as described in item χ of the patent claim 'wherein, eight) is a polymer made from vinyl aromatic monomers and their chlorinated forms. Acrylonitrile_Butadiene_Styrene Copolymer / Polycarbon 10__ Purpose composition, streak-free oxyether polymer, polybenzyl adduct, polyethylene terephthalate, epoxy Resin, ethylene glycol copolymer, ethylene acrylic acid copolymer] «hydrocarbon-carbon oxide heteropolymer, polyolefin, cyclic roasted hydrocarbon copolymer, olefinic copolymer and homopolymer, polyphenylene group A group of oxygen and any mixture of them. 15 3. The flame retardant polymer composition containing no element as described in item 2 of the patent, wherein A) is selected from styrene-butadiene block copolymer, polystyrene, φ South Impact polystyrene, acrylonitrile-butadiene-styrene copolymer, and styrene-acrylonitrile copolymer. 4. For example, the flame retardant polymer composition 20 without tooth element in the scope of patent application item i, wherein A) is 40 to 94 weight of the total weight of the flame retardant polymer composition without element I. %; B) is 1 to 30% by weight; and 0) is $ to 30% by weight. 5. Such as the scope of patent application! The self-priming flame-retardant polymer composition of the item, wherein B) is a modified multifunctional epoxy resin, which is derived from a polyfunctional epoxy resin selected from the following structure: 31 200538502 -Jn wherein "R" is hydrogen, CrQ alkylhydroxy, or CpCs alkyl, for example, methyl; and "η" is an integer of 0 or 1 to 10, and "η" preferably has an average value of 0 to 5 ; 5 wherein Gly is glycidyl; and 6. The halogen-free flame-retardant polymer composition according to item 1 of the scope of the patent application, wherein the modified polyfunctional epoxy resin has more than one ring from 32 200538502 per molecule. Material made from epoxy resin. 7. The halogen-free flame-retardant polymer composition according to item 1 of the patent application scope, wherein the modified polyfunctional epoxy resin has functionalities modified with more than one modifier. 5 8. The halogen-free flame-retardant polymer composition according to item 1 of the scope of patent application, wherein the modified polyfunctional epoxy resin contains less than 15% by weight of residual epoxy groups, which is Based on the total weight of the epoxy resin. 9. For example, a flame-retardant polymer composition containing no halogen in the scope of patent application, wherein the modified polyfunctional epoxy resin contains less than 12% by weight of 10% of residual epoxy groups, which Based on the total weight of the epoxy resin. 10. If the halogen-free flame-retardant polymer composition of item 9 of the patent application scope, wherein the modified polyfunctional epoxy resin contains less than 10% by weight of residual epoxy groups, it is based on The total weight of the epoxy resin. 11. For example, the halogen-free flame-retardant polymer composition 15 in the scope of the patent application is basically composed of the following: A) 40 to 94% by weight (based on the total weight of the composition) Thermoplastic polymer, optionally comprising 10 to 35% by weight (based on the total weight of the composition) of a polyphenylene ether polymer; B) 1 to 30% by weight (based on the total weight of the composition) ) Modified 20-functional polyfunctional epoxy resin, which contains 0-20% by weight (based on the total weight of the epoxy resin) of residual epoxy groups; and C) 5 to 30% by weight (based on the Phosphorus compounds such as aryl phosphates based on the total weight of the composition. 12. For example, the flame retardant polymer composition containing no S element in the scope of patent application No. 33 200538502, wherein the thermoplastic polymer of A) is selected from the group consisting of vinyl aromatic monomer and its hydrogenation type. Polymer, polycarbonate, acrylonitrile-butadiene-styrene / polycarbonate composition, polyphenylene ether resin, hydroxyphenoxy ether polymer, polyethylene terephthalate, epoxy Resin, copolymer of ethylene vinyl alcohol, ethylene acrylic acid copolymer, polyolefin carbon monoxide heteropolymer, polyolefin, cyclic olefin copolymer, olefin copolymer and homopolymer, and any mixture thereof Ethnic group. 13. For example, a halogen-free flame-retardant polymer composition according to item 12 of the application, wherein the thermoplastic polymer of A) is selected from the group consisting of styrene-butadiene 10-stage copolymer, polystyrene, High impact polystyrene, acrylonitrile-butadiene-styrene (ABS) copolymer, and styrene-acrylonitrile copolymer. 14. For example, the halogen-free flame-retardant polymer composition according to item 11 of the application, wherein the modified polyfunctional epoxy resin is an epoxy resin having an average of more than one epoxy group per molecule. Material made of epoxy resin. 15 15. The halogen-free flame-retardant polymer composition according to item 11 of the patent application scope, wherein the modified polyfunctional epoxy resin has functionalities modified with more than one modifier. 16. For example, the halogen-free flame-retardant polymer composition according to item 11 of the application, wherein the modified polyfunctional epoxy resin contains less than 15% by weight and 20% of residual epoxy groups, which is Based on the total weight of the epoxy resin. 17. The halogen-free flame-retardant polymer composition according to item 16 of the application, wherein the modified polyfunctional epoxy resin contains less than 12% by weight of residual epoxy groups, which is based on The total weight of the epoxy resin. 18. For example, the halogen-free flame-retardant polymer group 34 200538502 of the scope of application for the patent, wherein the modified multifunctional epoxy resin contains less than 18% by weight of residual epoxy groups, It is based on the total weight of the epoxy resin. 19. An article produced from a flame-retardant polymer composition containing no halogens in the scope of claims 1 or 18. 35 200538502 (1) Designated representative map: (1) The designated representative map in this case is: (). (None) (II) Brief description of the element representative symbols of this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: