WO2017073070A1 - Environmentally friendly flame-retardant composition and molding material that are based on thermoplastic impact-modified styrene polymer - Google Patents

Abstract

The present invention provides a halogen-free highly flame-retardant impact-modified resin in which V-O of the UL-94 standard is achieved in a thin material. The present invention achieves high flame retardancy in a thin material through a halogen-free flame-retardant resin composition containing (A) an impact-modified styrene resin, (B) aluminum hypophosphite, (C) an aromatic phosphoric acid ester, and (D) a drip inhibitor. In one embodiment, the aromatic phosphoric acid ester is resorcinol bis(di-2,6-xylylphosphate). In one embodiment, (D) is a polytetrafluoroethylene-based resin.

Description

Environmentally friendly flame retardant compositions and molding materials based on thermoplastic impact modified styrenic polymers

The present invention relates to an environment-friendly flame-retardant molding material based on a thermoplastic impact-resistant styrenic polymer.

The chemical composition of the organic polymer can be easily combusted. Therefore, various flame retardants are usually blended into polymers in order to meet stringent flame retardant standards required by processors and set by national and international organizations.

Recently, halogen-free flame retardants are used because of safety to the environment, although they are generally more expensive than brominated flame retardants used previously. Therefore, the importance of halogen-free flame retardants in the thermoplastic polymer market is increasing. The basic requirements for these products include: compounding, good processability in molding conditions, good mechanical and electrical properties in the solid state, no blooming or discoloration during or after molding, reinforced polymer And good flame retardancy in both non-reinforced polymers.

Pure polystyrene is hard but brittle. For example, a product with higher impact characteristics can be obtained by modifying with a rubber such as polybutadiene rubber. Accordingly, an impact-modified styrenic polymer is obtained.

The impact-modified styrenic polymer can be described as including rubber particles dispersed as an additional phase in a continuous, rigid styrene resin continuous phase. Since the surface tension of the interface between the two polymers is different, it is difficult to finely disperse the rubber phase into the thermoplastic continuous phase by melt mixing through an extruder. The impact properties of products containing well dispersed rubber are generally much better than those of products containing poorly dispersed rubber.

By adding rubber during the polymerization of the styrene phase, some graft copolymer chemically bonded to the polystyrene phase can be formed, which can act to homogenize the rubber itself. The polymerization can be carried out in bulk, emulsification or suspension of monomers.

The impact-improved styrene polymer is also known as a rubber-modified styrene polymer, and some well-known examples include high impact polystyrene (HIPS) and acrylonitrile butadiene styrene copolymer (ABS).

Impact-modified styrenic polymers are widely used for electronic devices and consumer products such as computer consoles, televisions, mobile phones, computers, stereos, toys and many others.

HIPS and ABS are commercially available and are produced by well-known methods.

Flame retardant HIPS and ABS are obtained using a bromine compound as a flame retardant. This is because they have the ability to maintain the good mechanical properties (eg, impact resistance) of the polymers. The most widely used flame retardants for ABS and HIPS are ethylene bistetrabromophthalimide, decabromodiphenylethane, brominated epoxy oligomers and tetrabromobisphenol A. Antimony oxide can be used as a synergist. However, bromine compounds need to be replaced because of restrictions on the use of halogen flame retardants.

For example, organic aryl phosphorus compounds as shown below are used in HIPS as some commercially available non-halogen flame retardants (in place of bromine flame retardants).

Resorcinol bis (diphenyl phosphate)
Bisphenol A bis (diphenyl phosphate)
Polymeric biphenyl phosphate Diphenyl cresyl phosphate Triphenyl phosphate.

However, these organic aryl phosphorus flame retardants do not satisfy the high standard regarding flame retardancy, that is, V-0 of UL-94, and actually give results only as V-2.

Polymer manufacturers have so far not succeeded in obtaining flame retardants for halogen-free HIPS and ABS that meet high flame retardant standards, ie, UL-94 V-0.

HIPS halogen-free flame retardant material that meets high flame retardant standards is made from a blend of high impact styrene polymer and phenyl ether polymer and is commercially available. Phenyl ether polymers are characterized by a high level of intrinsic flame retardancy. These polymer compositions are simply referred to as “HIPS” or more precisely “HIPS / PPO”. Commercially available phenyl ether polymers belong to two different types: polyphenylene ether (PPE) and polyphenylene oxide (PPO). PPE and PPO have similar chemical compositions and are generally treated as equivalent materials, and both are commonly referred to as PPO. They are difficult to process polymers and face many difficulties in molding operations compared to pure HIPS resins, despite blending polystyrene or HIPS to make the resin composition easier to process. . Moreover, PPO itself is generally more expensive than HIPS resin. The HIPS / PPO blend is not the object of the present invention.

ハ ロ ゲ ン ABS halogen-free flame retardant products that meet high flame retardant standards are made from blends of ABS polymer and polycarbonate and are available from major manufacturers. Polycarbonate is characterized by a high level of intrinsic flame retardancy. These compositions are referred to as “PC / ABS”. Polycarbonate is a difficult-to-process polymer and despite the fact that blending ABS makes it easy to process the composition, it still faces some difficulties in the molding operation compared to pure ABS resin. To do. Moreover, polycarbonate itself is generally more expensive than ABS resin. PC / ABS blends are not in accordance with the present invention.

Patent Document 1 (CN1027746608A) is an environmentally friendly flame retardant comprising at least one flame retardant aid selected from polyethylene wax, calcium stearate, pentaerythritol, melamine cyanurate and ammonium polyphosphate, and aluminum hypophosphite. A soluble ABS resin is disclosed. However, these compositions lack sufficient flame retardant properties, and in particular do not reach V-0 at 1.6 mm thickness in the UL-94 standard.

Patent Document 2 (CN103113708A) describes an ABS flame retardant resin in which the flame retardant is a combined use of an organic phosphite or hypophosphite and a synergized ammonium salt. However, even in this case, these compositions lack sufficient processability and produce flames and smoke during the mixing process.

Patent Document 3 (Japanese Patent Laid-Open No. 2002-161211) discloses a flame retardant resin composition containing various thermoplastic resins in which a flame retardant is a combination of an organic phosphite or a hypophosphite and a phosphate ester. In the paragraph 0026, regarding the preferred range of the weight ratio of the polyester resin (A-1) or polyamide resin (A-3) and the polystyrene resin (A-2), “the blending ratio (weight ratio) in the above combination is: , (A-1) / (A-3), (A-1) / (A-2) and (A-3) / (A-2) are preferably 100/0 to 5/95, more preferably Is in the range of 100/0 to 10/90, more preferably 100/0 to 30/70. Within this range, flame retardancy, heat resistance and impact resistance can be maintained at a high level. is doing. That is, it is explained that the ratio of the polystyrene resin (A-2) is preferably up to 95%, more preferably up to 90%, and even more preferably up to 70%. That is, if the ratio of polystyrene resin is up to 95%, the flame retardancy is maintained at a preferable level, and if the ratio of polystyrene resin is up to 90%, the flame retardancy is maintained at a more preferable level. If the ratio is up to 70%, it is described that the flame retardancy is maintained at a more preferable level. However, it is not described here that very favorable flame retardant standards such as UL-94 V-0 can be achieved at such preferred weight ratios. Specifically, the examples disclose only a mixture of a small amount (10%) of an ABS resin and a large amount (90%) of another resin with calcium hypophosphite and a large amount of glass fiber. In addition, it is not disclosed to achieve V-0 of UL-94 in a resin composition mainly composed of an impact-modified styrene resin.

Further, regarding the description of the above-mentioned paragraph 0026 of Patent Document 3, the degree to which a smaller amount is preferable when focusing on the polystyrene-based resin (A-2) is increased, and the implementation of Patent Document 3 In view of the fact that in the example, only a composition containing only 10% by weight of the polystyrene resin (A-2) is disclosed, as a whole of Patent Document 3, “the ratio of polystyrene resin is: It is understood that less is preferred ".

Patent Document 3 does not particularly disclose achieving V-0 of UL-94 in a resin composition that does not contain a large amount of glass fiber.

That is, it is very difficult to achieve high flame retardancy in a thermoplastic resin composition containing an impact-modified styrene resin as a main component. Specifically, at a weight ratio as described in paragraph 0026, Unable to achieve very strict flame retardance standards like UL-94 V-0, as shown in the examples, the amount of styrenic resin must be reduced to 10% and a large amount of glass fiber added. UL-94 V-0 cannot be achieved. According to the invention of Patent Document 3, flame retardancy could not be achieved in a thermoplastic resin composition containing an impact-modified styrene resin as a main component.

Chinese Patent Application No. 1027746608 Chinese Patent Application No. 103113708 JP 2002-161211 A

OBJECT OF THE INVENTION It is an object of the present invention to provide a halogen free, non-reinforced or reinforced high flame retardant styrene based impact modifying resin.

Another object of the present invention is to provide a halogen-free highly flame-retardant styrene-based impact-improving resin, which is a thin member and becomes V-0 of the international standard UL-94.

Again, another object of the present invention is to provide a halogen-free highly flame-retardant styrene-based impact-improving resin composition having a specimen thickness of preferably 3.2 mm or less, more preferably 1.6 mm, and V-0. It is.

Yet another object of the present invention is to provide halogen free flame retardant molding compositions and products based on halogen free high flame retardant styrene impact modifying polymers having good aesthetic and mechanical properties. .

These and other objectives are achieved with the compositions and flame retardants of the present invention.

For example, the present invention provides the following composition and flame retardant.
(Claim 1)
Halogen-free flame retardant thermoplastic resin composition,
(A) thermoplastic resin,
(B) aluminum hypophosphite,
(C) an aromatic phosphate ester, and (D) an anti-drip agent,
50% by weight or more of the (A) thermoplastic resin is an impact-improved styrene resin,
Resin composition.
(Section 2)
Item 2. The resin composition according to Item 1, wherein 80% by weight or more of the thermoplastic resin (A) is an impact-improved styrene resin.
(Section 3)
Item 3. The resin composition according to Item 1 or 2, wherein the impact-modified styrene resin is an ABS resin.
(Claim 4)
Item 4. The resin composition according to any one of Items 1 to 3, wherein the (C) aromatic phosphate ester is an aromatic condensed phosphate ester.
(Section 5)
Item 4. The resin composition according to any one of Items 1 to 3, wherein (C) the aromatic phosphate ester is resorcinol bis (di-2,6-xylyl phosphate).
(Claim 6)
Item 6. The resin composition according to any one of Items 1 to 5, wherein the (D) anti-drip agent is a resin based on polytetrafluoroethylene.
(Claim 7)
Item 7. The weight ratio of (B) aluminum hypophosphite to (C) aromatic phosphate is (B) :( C) = 90: 10 to 60:40, Resin composition.
(Section 8)
Item 7. The weight ratio of (B) aluminum hypophosphite to (C) aromatic phosphate is (B) :( C) = 85: 15 to 65:35, Resin composition.
(Claim 9)
Item 7. The weight ratio of (B) aluminum hypophosphite and (C) aromatic phosphate is (B) :( C) = 80: 20 to 70:30, Resin composition.
(Section 10)
Item 7. The resin composition according to Item 6, wherein the amount of the anti-drip agent is 0.1 to 0.6% by weight of the resin composition.
(Item 11)
11. The resin composition according to any one of items 1 to 10, which does not contain glass fiber.
(Clause 12)
A flame retardant for flame retardant a halogen-free thermoplastic resin composition,
The thermoplastic resin composition is
(A) a thermoplastic resin, and (D) an anti-drip agent,
50% by weight or more of the (A) thermoplastic resin is an impact-modified styrene resin,
The flame retardant is
(B) aluminum hypophosphite, and (C) aromatic phosphate ester, wherein the weight of (C) aromatic phosphate ester is the sum of (B) aluminum hypophosphite and (C) aromatic phosphate ester A flame retardant that is 10% or more of the weight.
(Section 13)
The impact-modified styrenic resin is ABS or HIPS, the (C) aromatic phosphate is resorcinol bis (di-2,6-xylyl phosphate), the (B) aluminum hypophosphite and the (C The flame retardant according to item 12, wherein the weight ratio of the aromatic phosphate ester is (B) :( C) = 85: 15 to 65:35.
(Item 14)
Item 11. The resin composition according to any one of Items 1, 2, 4 to 10, wherein the impact-improved styrene resin is a high-impact polystyrene resin (HIPS).

Also, according to another aspect of the invention, these and other objects are:
A) at least one impact-modified thermoplastic styrenic resin,
B) As a first flame retardant component, a metal hypophosphite salt in which at least one phosphorus valence state is +1,
C) As second flame retardant component, at least one aromatic phosphate ester D) at least one anti-drip agent E) filler and / or reinforcing fiber F) achieved by a resin composition containing other conventional additives .

According to the present invention, high flame retardancy and easy moldability are achieved in a resin composition containing an impact-improved styrene resin as a main component.

DESCRIPTION OF THE INVENTION According to the present invention, the thermoplastic styrenic impact modifying polymer is preferably selected as ABS and / or HIPS.

Therefore, the object of the present invention is to provide impact-modified styrenic resins such as ABS and HIPS, metal hypophosphites (eg, aluminum hypophosphite), aromatic phosphate esters, anti-drip agents, and other conventional additives. Is a flame retardant composition based on

The metal hypophosphite is characterized in that the valence state of phosphorus is +1.

The metal hypophosphite has the following chemical formula:
Me (H ₂ PO ₂ ) _n
here,
n is an integer of 1 to 4 depending on the valence of the metal represented by Me, and the metal Me belongs to Groups I, II, III, and IV of the periodic table.

Aluminum hypophosphite has the following chemical formula:
Al (H ₂ PO ₂ ) ₃
Sodium hypophosphite and calcium hypophosphite are widely commercially available and are usually prepared by reaction of the corresponding metal hydroxide with yellow phosphorus, for example according to the following reaction scheme where Me is selected as calcium:
P ₄ + 2Me (OH) ₂ + H ₂ O
→ Me (H ₂ PO ₂ ) ₂ + MeHPO ₃ + PH ₃
Hypophosphorous acid metal salts other than calcium and sodium are usually produced by the reaction of the corresponding metal hydroxide with hypophosphorous acid or the exchange reaction of the corresponding metal salt (see, for example, “Hypophosphorus Acid and it salts, Russian Chemical”). Review, 44 (12), 1975 "). Aluminum hypophosphite can also be produced using this method.

Accordingly, the present invention relates to a halogen-free flame retardant composition, essentially comprising an impact modified styrenic resin, at least one metal hypophosphite salt, at least one aromatic phosphate ester as a flame retardant, and at least one drip prevention. As well as other conventional additives.

Such a composition has high flame retardancy and easy moldability.

Particularly preferably, the impact-modified styrenic resin is selected as ABS or HIPS, the metal hypophosphite is selected as aluminum hypophosphite, and the aromatic phosphate is resorcinol bis (di-2,6-xylylphosphate). Selected, anti-drip agents and other conventional additive compositions such as fillers, pigments, thermal stabilizers and processing stabilizers.

According to the present invention, other conventional additives are selected from processability improvers, heat and processing stabilizers, UV stabilizers, pigments, dispersants, mold release agents, crystal nucleating agents, and mixtures thereof. obtain.

According to the present invention, the metal hypophosphite has a phosphorus valence of +1 and is preferably aluminum hypophosphite.

According to the present invention, the aromatic phosphate ester which is a flame retardant is preferably resorcinol bis (di-2,6-xylyl phosphate).

In the following, further aspects of the invention will be described in more detail.

A) Thermoplastic resin In the resin composition of the present invention, a halogen-free thermoplastic resin is used.

In the resin composition of the present invention, an impact-modified styrene resin is used as the main component of the thermoplastic resin.

The amount of the impact-improved styrene resin is preferably 30% by weight or more of the total weight of the thermoplastic resin. More preferably, the amount of the impact-modified styrene resin is 40% by weight or more of the total weight of the thermoplastic resin. More preferably, the amount of the impact-modified styrene resin is 50% by weight or more of the total weight of the thermoplastic resin. If necessary, the amount of impact-modified styrenic resin may be 55% by weight or more of the total weight of the thermoplastic resin, 60% by weight or more, and 65% by weight or more. 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, It may be 95% by weight or more, or 100% by weight.

When the resin composition contains a large amount of impact-modified styrene resin, it is disadvantageous in terms of flame retardancy. However, in the present invention, high flame retardancy is achieved even when the resin composition contains a large amount of impact-modified styrene resin.

When a thermoplastic resin other than the impact-improved styrene resin is used for the resin composition of the present invention, any conventionally known thermoplastic resin other than the impact-improved styrene resin can be used as the thermoplastic resin. .

A1) Impact-modified styrene resin (for example, ABS or HIPS)
As the impact-modified styrene resin, any conventionally known impact-modified styrene resin can be used.

HIPS is prepared by dispersing a polymerized rubber phase into a styrene monomer and polymerizing styrene into a thermoplastic phase in the presence of rubber and a grafting agent. The rubber is partially crosslinked and separates from the mixture as the molecular weight of styrene increases. In some embodiments, the rubber includes a grafted styrene monomer such as SBR (styrene butadiene rubber). The amount of grafting between the rubber and the thermoplastic phase varies and depends on the application.

ABS is prepared by dispersing a polymerized rubber phase in styrene and acrylonitrile monomers and copolymerizing styrene and acrylonitrile in the presence of rubber and a grafting agent. The rubber partially crosslinks and separates as the molecular weight of the styrene / acrylonitrile copolymer increases. The rubber is typically a butadiene type rubber, but is selected from a copolymer of styrene, acrylonitrile and alkyl acrylate, a copolymer of butadiene and styrene, and an isoprene type rubber. In some embodiments, the rubber includes a styrene monomer such as SAN (styrene acrylonitrile rubber) and a grafted monomer of acrylonitrile. The amount of grafting between the rubber and the thermoplastic phase varies and depends on the application.

B) Aluminum hypophosphite The selection of the most appropriate hypophosphite depends on several important factors. Particularly suitable hypophosphites have sufficient thermal stability to withstand melt processing at temperatures above 200 ° C. If they form hydrates, they are used in the corresponding anhydrous form and should not absorb moisture when they are later exposed to ambient humidity. Examples of hypophosphites include aluminum hypophosphite (CAS7784-22-7), calcium hypophosphite (CAS7789-79-9), manganese hypophosphite (CAS10043-84-2), magnesium hypophosphite (CAS10377-). 57-8), zinc hypophosphite (CAS15060-64-7), and barium hypophosphite (CAS171258-64-3). Most preferred according to the invention is aluminum hypophosphite.

Aluminum hypophosphite with a chemical structure of Al (H ₂ PO ₂ ) ₃ is a different particle suitable for thermoplastic processing with low water absorption and high purity, for example, by Ilatch Chemical Spa (product name: Phoslite IP-A). Widely manufactured as a white powder with a diameter distribution.

Aluminum hypophosphite is a flammable powder, like many anhydrous hypophosphites, for easy transportation and handling, as a dry mix with other solid flame retardants, or in masterbatch form Sold.

Thus, since aluminum hypophosphite is a flammable powder, there is a drawback that it is not easy to transport and handle. For this reason, aluminum hypophosphite has not been considered a preferred material as a flame retardant. It has not been easy for those skilled in the art to select aluminum hypophosphite as a flame retardant.

In the present invention, aluminum hypophosphite shows very good performance. Thus, in one embodiment, the resin composition or flame retardant is substantially free of hypophosphites other than aluminum hypophosphite.

C) Aromatic Phosphate Ester In the present invention, any conventionally known aromatic phosphate ester can be used as the aromatic phosphate ester.

For example, preferred aromatic phosphate esters can be shown as the following general chemical structure.

(In the formula, R ₁ , R ₂ , R ₃ , R ₁ ′, R ₂ ′, R ₃ ′, R ₁ ″, R ₂ ″, R ₃ ″, R ₁ ″ ″, R ₂ ″ ', R ₃ ''' are each independently selected from H (hydrogen) or C ₁ to C ₄ (C ₁ -C 4) alkyl group, X is selected from a C ₆ aryl group or a diphenylmethane derivative; n is an integer from 0 to 7.)
For example, when n = 0, examples include triphenyl phosphate, tri (2,6-dimethylphenyl) phosphate, and combinations thereof.

For example, when n = 1 to 7 and X is an aryl group, examples include resorcinol bis (diphenyl phosphate) or resorcinol bis (di-2,6-xylyl phosphate).

For example, when n = 1 to 2 and X = (CH ₃ ) ₂ C (C ₆ H ₄ ) ₂ , examples include bisphenol A bis (diphenyl phosphate).

Preferred aromatic phosphates that act as flame retardants of the present invention are solid at room temperature, that is, those having a melting point higher than 40 ° C., more preferably those having a melting point higher than 80 ° C.

According to the present invention, one example of an aromatic phosphate ester is resorcinol bis (di-2,6-xylyl phosphate) (RDX) having the following chemical structure:
(Resorcinol bis (di-2,6-xylyl phosphate) (RDX))

Compared to liquids, solid phosphate esters are advantageous for the purposes of the present invention. This is because solid phosphoric acid ester can be mixed with hypophosphite, which is a combustible solid in powder form, and suppresses the combustibility of the mixed powder. The handling of non-flammable powders is actually advantageous in terms of safety, equipment and operational complexity. Therefore, the mixed use of aromatic phosphate ester and hypophosphite facilitates the handling and processing of the compound and the industrial process in producing the flame retardant halogen-free styrene impact strength improved resin composition of the present invention.

In the resin composition of the present invention, the total weight of (B) aluminum hypophosphite and (C) aromatic phosphate is preferably 5 parts by weight or more with respect to 100 parts by weight of the total thermoplastic resin, More preferably, it is 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, and particularly preferably 25 parts by weight or more, particularly preferably 30 parts by weight. More than a part. The total weight of (B) aluminum hypophosphite and (C) aromatic phosphate is preferably 65 parts by weight or less, more preferably 60 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Part or less, more preferably 55 parts by weight or less, still more preferably 50 parts by weight or less, particularly preferably 45 parts by weight or less, and particularly preferably 40 parts by weight or less. Preferably, it is 35 parts by weight or less. The upper limit is not limited from the viewpoint of flame retardancy, but if it is too much, the physical properties of the resin composition may deteriorate.

In the flame retardant and resin composition of the present invention, of the total weight of (B) aluminum hypophosphite and (C) aromatic phosphate ester, the amount of (B) aluminum hypophosphite is preferably 60% by weight or more. More preferably, it is 65% by weight or more, more preferably 70% by weight or more, still more preferably 71% by weight or more, and particularly preferably 72% by weight or more, particularly preferably 73 wt% or more, and most preferably 74 wt% or more. Of the total weight of (B) aluminum hypophosphite and (C) aromatic phosphate, the amount of (B) aluminum hypophosphite is preferably 95% by weight or less, more preferably 90% by weight or less. More preferably, it is 85% by weight or less, more preferably 80% by weight or less, particularly preferably 78% by weight or less, particularly preferably 77% by weight or less, most preferably 76% by weight or less.

In a highly preferred embodiment, of the total weight of (B) aluminum hypophosphite and (C) aromatic phosphate ester, the amount of (B) aluminum hypophosphite is 75% by weight. When the amount of (B) aluminum hypophosphite is close to 75% by weight, the flame retardant and the resin composition exhibit extremely excellent characteristics.

D) Anti-drip agent In the present invention, a conventionally known anti-drip agent may be used as the anti-drip agent (anti-dripping agent).

Polytetrafluoroethylene (PTFE) is widely used as an anti-drip agent in flame retardant resin compositions that meet the required UL-94 V-0 or similar standards. The high molecular weight PTFE component forms microfibrils under shear conditions during resin molding. The squeezed fibrils create a network that is physically immobilized in the resin matrix. Fibril relaxation during resin combustion causes a wide range of resin shrinkage and drip suppression.

High molecular weight PTFE is useful for drip suppression, but sometimes difficult to handle due to its tendency to agglomerate, making industrial scale handling difficult.

Specially modified grades such as PTFE modified with acrylic or PTFE coated with styrene acrylonitrile (SAN) called “TSAN” can guarantee excellent powder flowability and high dispersion efficiency. Such products are individually described, for example, in EP0758010A1 or WO03062291A1.

The anti-drip additive is usually used in the range of 0.1 to 0.6% by weight of the resin composition. The amount of the anti-drip agent is preferably 0.15% by weight or more of the resin composition, 0.20% by weight or more, or 0.25% by weight or more. The amount of the anti-drip agent is preferably 0.55% by weight or less of the resin composition, may be 0.5% by weight or less, may be 0.45% by weight or less, It may be not more than wt%, or may be not more than 0.35 wt%.

E) Filler and / or reinforcing fiber The resin composition of the present invention may contain fibers (for example, reinforcing fibers) as necessary. Any known fiber may be used as the fiber. Organic fibers (for example, carbon fibers) can also be used, and inorganic fibers (for example, glass fibers) can also be used.

The amount of fiber (organic fiber or inorganic fiber) used is not particularly limited. For example, the amount of fiber used may be 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more with respect to 100 parts by weight of the total thermoplastic resin. 2 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, It may be 25 parts by weight or more, or 30 parts by weight or more. Moreover, it may be 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more as required. The amount of fiber used may be 100 parts by weight or less, 90 parts by weight or less, or 80 parts by weight or less, with respect to 100 parts by weight of the thermoplastic resin. It may be 70 parts by weight or less, 60 parts by weight or less, or 50 parts by weight or less.

When the resin composition contains a large amount of inorganic fibers, it is advantageous in flame retardancy. When the resin composition contains only a small amount of inorganic fibers, it is disadvantageous in flame retardancy. However, in the present invention, even when the resin composition contains only a small amount of inorganic fibers (for example, when the amount is less than or less than the upper limit listed above), or when the resin composition does not contain inorganic fibers, it is highly difficult. Flammability is achieved. That is, an embodiment in which the content of the inorganic fiber is less than any of the above-listed upper limits, or an even smaller embodiment, for example, an embodiment in which the total amount of thermoplastic resin is 40 parts by weight or less with respect to 100 parts by weight. 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight In an embodiment that is less than or equal to parts, and an embodiment in which the content is 0, the present invention provides a composition that can achieve high flame retardancy.

Examples of preferable reinforcing fibers used in the present invention are carbon fibers, aramid fibers, and preferably glass fibers used in the form of commercially available chopped glass. In order to improve the compatibility with the thermoplastic resin, the surface of the reinforcing fiber may be treated with a silane compound (for example, a silane coupling agent). The reinforcing fibers can be used in the above-mentioned amounts, but can preferably be used in the range of, for example, 10% to 50% by weight, more preferably 20% to 35% by weight of the resin composition. When the amount is small, the advantage of mechanical properties is small, and when it exceeds 50% by weight, the melt viscosity becomes very high.

The resin composition of the present invention may contain a filler as necessary.

Examples of fillers that can be used in the present invention are glass beads, hollow glass spheres, amorphous silica, chalk, mica, calcined kaolin, wollastonite, talc, magnesium carbonate, barium sulfate or similar products and they are fatty acids or similar Those obtained by surface treatment with a compound or pulverized in the presence of a fatty acid or a similar compound. Any fine particles widely sold in the market as fillers for thermoplastic resins may be used in the composition of the present invention as long as the average particle size of the powder measured by laser is in the range of 2 to 20 microns. .

The amount of filler (for example, inorganic filler) used is not particularly limited. For example, it may be 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight with respect to 100 parts by weight of the total thermoplastic resin. Part or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight May be 30 parts by weight or more. Moreover, it may be 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more as required. And the usage-amount of a filler (for example, inorganic filler) may be 100 weight part or less with respect to a total of 100 weight part of a thermoplastic resin, may be 90 weight part or less, and may be 80 weight part or less. May be 70 parts by weight or less, 60 parts by weight or less, or 50 parts by weight or less.

When the resin composition contains a large amount of inorganic filler, it is advantageous in flame retardancy. When the resin composition contains only a small amount of an inorganic filler, it is disadvantageous in flame retardancy. However, in the present invention, even when the resin composition contains only a small amount of inorganic filler (for example, when it is less than the above-listed upper limit or when it is further less), or when it does not contain an inorganic filler, it is highly difficult. Flammability is achieved. That is, an embodiment in which the content of the inorganic filler is less than any of the above-listed upper limits, or an embodiment having a smaller content, for example, 40 parts by weight or less with respect to a total of 100 parts by weight of the thermoplastic resin. 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight In an embodiment that is less than or equal to parts, and an embodiment in which the content is 0, the present invention provides a composition that can achieve high flame retardancy.

F) Other conventional additives The novel flame retardant compositions based on impact-modified styrenic resins according to the invention may contain one or more other conventional additives. The additive may be an organic additive or an inorganic additive. Such conventional additives include, for example, the following compounds:
Partially crosslinked elastomeric polymers used as processing aids, heat and processing stabilizers, UV stabilizers, pigments, dispersants, mold release agents, crystal nucleating agents, impact modifiers, and mixtures thereof.

The amount of conventional additives (for example, inorganic additives) used is not particularly limited. For example, it may be 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, or 2 parts by weight with respect to a total of 100 parts by weight of the thermoplastic resin. Part or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight May be 30 parts by weight or more. Moreover, it may be 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more as required. And the usage-amount of a conventional additive (for example, inorganic additive) may be 100 weight part or less with respect to a total of 100 weight part of a thermoplastic resin, and may be 90 weight part or less. 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, or 50 parts by weight or less.

When the resin composition contains a large amount of an inorganic additive, it is advantageous in terms of flame retardancy. When the resin composition contains only a small amount of an inorganic additive, it is disadvantageous in flame retardancy. However, in the present invention, even when the resin composition contains only a small amount of an inorganic additive (for example, when it is less than the above-listed upper limit or when it is further less), or when it does not contain an inorganic additive, High flame retardancy is achieved. That is, an embodiment in which the content of the inorganic additive is less than any of the above-listed upper limits, or an even smaller embodiment, for example, 40 parts by weight or less with respect to a total of 100 parts by weight of the thermoplastic resin. Embodiment, embodiment of 30 parts by weight or less, embodiment of 20 parts by weight or less, embodiment of 10 parts by weight or less, embodiment of 5 parts by weight or less, embodiment of 3 parts by weight or less, or 1 In an embodiment in which the content is not more than parts by weight, and in an embodiment in which the content is 0, the present invention provides a composition that can achieve high flame retardancy.

The following experimental examples are given as non-limiting examples.

Experimental Part In the examples below, the ingredients listed below were used.
resin:
ABS (Magnum ABS 3904, manufactured by STYRON), hereinafter referred to as ABS.

HIPS (Edistir SR 550, manufactured by Enchem Versalis), hereinafter referred to as HIPS.
Reinforcing fiber:
Glass fiber (PPG3786, manufactured by PPG), hereinafter referred to as GF.
Stabilizer:
Hindered phenol heat stabilizer (Irganox 1010, manufactured by BASF), hereinafter, Irg. Indicated as 1010.

Phosphorous acid processing stabilizer (Irgaphos 168, manufactured by BASF), hereinafter, Irg. Indicated as 168.
Hypophosphite:
Aluminum hypophosphite (Phoslite IP-A, manufactured by Italmatch Chemical), hereinafter referred to as IP-A.

Aromatic phosphate ester:
Resorcinol bis (di-2,6-xylyl phosphate) (PX-200, manufactured by Daihachi Chemical Industry), hereinafter referred to as RDX.
Anti-drip agent:
Fluorinated copolymer (Dyneon MM 3595, manufactured by 3M), hereinafter referred to as PTFE.

Flame retardant for comparative examples not according to the invention:
Calcium hypophosphite (Phoslite IP-C, manufactured by Italmatch Chemical), hereinafter referred to as IP-C.
Melamine cyanurate (Melagard MC25, manufactured by Ital Match Chemical), hereinafter referred to as MC.
Ammonium polyphosphate (Exolit AP 422, manufactured by Clariant), hereinafter referred to as APP.
A lubricant polyethylene wax (Kemfluid 201, manufactured by UNION DERIVAN, SA) considered for the comparative example, hereinafter referred to as PEwax.
Calcium stearate (Kemistab EC, UNION DERIVAN, manufactured by SA), hereinafter referred to as CaStear.
Another additive for the comparative example, pentaerythritol (Charmor PM40, manufactured by Perstorp), hereinafter referred to as PERT.
Ammonium sulfate (reagent grade), hereinafter expressed as (NH ₄ ) SO ₄ .
Ammonium chloride (reagent grade), hereinafter denoted as NH ₄ Cl.

Examples according to the present invention (Examples 6 to 9) and comparative examples (Comparative Examples 1 to 5, Comparative Examples 10 to 17)
All the components shown in Table 1 were mixed in a twin screw extruder with a diameter of 20 mm at a temperature in the range of 220-230 ° C. The pellets were injection molded to different thicknesses, and five test pieces were subjected to conditions of 23 ° C. and 50% humidity for 24 hours. Flame retardancy was reported according to the UL-94 procedure. If the test did not reach V-0, V-1, or V-2, the NC type was given. If the sample could not be extruded or injected, it was classified as NP.

Table 1 (Examples and Comparative Examples)

* NC: V-0, V-1, and V-2 were not reached.

NP: Could not be molded.

* NC: V-0, V-1, and V-2 were not reached.

NP: Could not be molded.

Explanation of Table 1 Examples (Examples 6 to 9) and Comparative Examples (Comparative Examples 1 to 5) of the present invention
Comparative Example 1 in which only 35% of IP-A was added as a flame retardant did not reach UL-94 V-0 at 1.6 mm. Comparative Example 2 containing only 25% of RDX could not be processed. Comparative Example 3 containing 20% RDX alone was not effective with UL-94. Comparative Example 4 of the mixture of IP-A and RDX was UL-94 of 1.6 mm and V-2 did not reach V-0. Comparative Example 5 of the resin composition containing IP-A in the presence of PTFE did not reach V-0 of UL-94 at 1.6 mm.

Examples 6 and 9 of the present invention, which are the same combination of IP-A, RDX and PTFE, reached V-0 of UL-94 at 1.6 mm for both ABS and HIPS.

Example 7 of the present invention showing a combination of IP-A, RDX and PTFE gave a resin composition that reached V-0 of UL-94 even in the presence of glass fiber.

Example 8 using a combination of IP-A, RDX and PTFE without using a stabilizer was effective, and reached UL-094 V-0 at 1.6 mm.

Explanation of Table 1, Comparative Examples 10 to 14 (CN1027746608A)
Comparative Examples 10 to 14 showing combinations of aluminum hypophosphite (IP-A) and other elements described as auxiliaries described in CN10275606608A did not reach V-0 of UL-94 or molded Could not process.

Explanation of Table 1, Comparative Examples 15 and 16 (CN103113708A)
Comparative Examples 15 and 16 showing the combination of aluminum hypophosphite (IP-A) and ammonium salt described in CN103113708A could not be molded.

As described above, the resin composition described in CN1027746608A and CN103113708A does not reach V-0 even with a test piece of 1.6 mm or 3.2 mm. .

On the contrary, the difference between the composition according to the present invention and the composition according to the prior art is that the flame retardant resin composition according to the present invention reaches V-0 in the UL-94V test when the thickness is 3.2 mm.

Explanation of Table 1, Comparative Example 17 (Japanese Patent Laid-Open No. 2002-161211)
Japanese Patent Application Laid-Open No. 2002-161211 describes various thermoplastic resins in the claims, and in the 0026 paragraph, it is described that flame retardance can be maintained at a high level when the amount of polystyrene resin is small. . The resin described in the examples is only a mixture of 90% other resin and 10% ABS. Although it has been disclosed that when calcium hypophosphite, RDX and GF are added to this resin mixture, V-0 is reached at 3.2 mm. However, when ABS resin is the main component resin or ABS resin is used alone Performance is not shown when doing so. As shown in Comparative Example 17, when the resin component blended in Example 1 was only ABS resin, V-0 was not obtained even at 3.2 mm. In the invention of Japanese Patent Laid-Open No. 2002-161211, it is understood that V-0 of UL-94 cannot be achieved in a resin composition containing an impact-improved styrene resin as a main component.

(Comparative Examples 18 to 19 and Examples 20 to 21)
The ingredients shown in Table 2 are uniformly mixed in a high speed laboratory mixer into a non-flammable, void-free, low thermal conductive base plate in a continuous strip or powder array of 250 mm long, 20 mm high and 10 mm high. Been formed. The powder or granular material was loosely filled into a mold having a triangular cross section of 250 mm long, 10 mm high and 20 mm wide. The mold was then dropped three times from a height of 2 cm from the solid surface. The mold was then refilled if necessary. Then remove the side restrictions and remove the excess. A non-combustible, void-free base plate with low thermal conductivity was placed on the mold, and the mold was turned upside down. A flame from a gas burner (5 mm in diameter) was applied to one end of the powder row until it ignited or for a maximum of 2 minutes. If the powder did not ignite or combustion with flames and smolders did not propagate through the 200 mm row of powder in 4 minutes (or 40 minutes), the material was considered non-flammable. When the powder burned, the burning time was reported.

As understood from Comparative Examples 18 and 19, there is a problem of flammability when aluminum hypophosphite is used alone or in high purity. As understood from Examples 20 and 21 above, the problem is solved by mixing with a substantial amount of an aromatic phosphate.

An object of the present invention is to provide a halogen-free highly flame-retardant styrene impact-improving resin that achieves V-0 of the UL-94 standard with a thin material. The object is achieved by the composition of the present invention.

Accordingly, in one embodiment, the present invention provides:
(Item 1) Halogen-free flame-retardant impact-modified styrene thermoplastic composition containing the following components:
A) At least one thermoplastic impact-modified styrene resin B) As a first flame retardant component, at least one phosphorus hypophosphite metal salt in which the valence state is +1 C) At least one second flame retardant component Two aromatic phosphates D) at least one anti-drip agent E) fillers and / or reinforcing fibers F) conventional additives.
(Item 2) The thermoplastic composition according to item 1, wherein the conventional additive is a heat and processing stabilizer, a UV stabilizer, a pigment, a dispersant, a release agent, a crystal nucleating agent, and a mixture thereof. object.
(Item 3) The thermoplastic composition according to Item 1 or Item 2, wherein the metal hypophosphite salt is aluminum hypophosphite.
(Item 4) The thermoplastic composition according to any one of Items 1 to 3, wherein the aromatic phosphate ester is resorcinol bis (di-2,6-xylenyl phosphate).
(Item 5) The thermoplastic composition according to any one of Items 1 to 4, wherein the anti-drip agent is polytetrafluoroethylene PTFE.
(Item 6) The thermoplastic composition according to any one of Items 1 to 5, wherein the styrene impact-improved thermoplastic resin is acrylonitrile butadiene styrene copolymer resin ABS. (Item 7) The thermoplastic composition according to any one of Items 1 to 6, wherein the styrene impact-modified thermoplastic resin is high impact polystyrene HIPS.
(Item 8) A flame retardant comprising the non-combustible powder mixture obtained by uniformly mixing the first flame retardant component and the second flame retardant component, wherein 8. A flame retardant for use in the thermoplastic composition according to any one of items 7 to 7.
(Item 9) Use of the flame retardant according to item 8 above as a flame retardant in a high impact polystyrene HIPS and / or acrylonitrile butadiene styrene copolymer ABS thermoplastic composition.
(Item 10) Use of the thermoplastic composition according to item 1 in the production of a flame retardant molding composition having good appearance and mechanical properties, and a product thereof.

As described above, the present invention has been exemplified using the preferred embodiment of the present invention, but the present invention should not be construed as being limited to this embodiment. It is understood that the scope of the present invention should be construed only by the claims. It is understood that those skilled in the art can implement an equivalent range based on the description of the present invention and the common general technical knowledge from the description of specific preferred embodiments of the present invention. Patents, patent applications, and documents cited herein should be incorporated by reference in their entirety, as if the contents themselves were specifically described herein. Understood.

Claims (14)

1. Halogen-free flame retardant thermoplastic resin composition,
   (A) thermoplastic resin,
   (B) aluminum hypophosphite,
   (C) an aromatic phosphate ester, and (D) an anti-drip agent,
   50% by weight or more of the (A) thermoplastic resin is an impact-improved styrene resin,
   Resin composition.
2. The resin composition according to claim 1, wherein 80% by weight or more of the thermoplastic resin (A) is an impact-modified styrene resin.
3. The resin composition according to claim 1 or 2, wherein the impact-modified styrene resin is an ABS resin.
4. The resin composition according to any one of claims 1 to 3, wherein the (C) aromatic phosphate ester is an aromatic condensed phosphate ester.
5. The resin composition according to any one of claims 1 to 3, wherein the (C) aromatic phosphate ester is resorcinol bis (di-2,6-xylyl phosphate).
6. The resin composition according to any one of claims 1 to 5, wherein the (D) anti-drip agent is a resin based on polytetrafluoroethylene.
7. The weight ratio of (B) aluminum hypophosphite to (C) aromatic phosphate is (B) :( C) = 90: 10 to 60:40, according to any one of claims 1 to 6. Resin composition.
8. The weight ratio of the (B) aluminum hypophosphite and the (C) aromatic phosphate ester is (B) :( C) = 85: 15 to 65:35. Resin composition.
9. The weight ratio of (B) aluminum hypophosphite to (C) aromatic phosphate is (B) :( C) = 80: 20 to 70:30. Resin composition.
10. The resin composition according to claim 6, wherein the amount of the anti-drip agent is 0.1 to 0.6% by weight of the resin composition.
11. The resin composition according to any one of claims 1 to 10, which does not contain glass fiber.
12. A flame retardant for flame retardant a halogen-free thermoplastic resin composition,
    The thermoplastic resin composition is
    (A) a thermoplastic resin, and (D) an anti-drip agent,
    50% by weight or more of the (A) thermoplastic resin is an impact-modified styrene resin,
    The flame retardant is
    (B) aluminum hypophosphite, and (C) aromatic phosphate ester, wherein the weight of (C) aromatic phosphate ester is the sum of (B) aluminum hypophosphite and (C) aromatic phosphate ester A flame retardant that is 10% or more of the weight.
13. The impact-modified styrenic resin is ABS or HIPS, the (C) aromatic phosphate ester is resorcinol bis (di-2,6-xylyl phosphate), the (B) aluminum hypophosphite and the (C The flame retardant according to claim 12, wherein the weight ratio of the aromatic phosphate ester is (B) :( C) = 85: 15 to 65:35.
14. 11. The resin composition according to claim 1, wherein the impact-modified styrene resin is a high impact polystyrene resin (HIPS).