JP2022070479A - Flame-retardant resin composition and molded product made from the same - Google Patents

Abstract

To provide a flame-retardant resin composition which can achieve high-degree flame retardancy even in a resin having particularly high heat resistance, and a molded product made from the same.SOLUTION: A flame-retardant resin composition contains (A) a thermoplastic resin (component A) and a pentaerythritol diphosphonate compound (component B) represented by the following formula (1), in which 1-50 pts.wt. of the component B is contained with respect to 100 pts.wt. of the component A. In the formula (1), R1, R2, R3 and R4 may be each independently the same, and are a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R5 and R6 may be each independently the same, and are a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a flame-retardant resin composition containing a pentaerythritol diphosphonate compound having a specific structure.

Resins such as polycarbonate resin, polyphenylene oxide resin, polyester resin, ABS resin, styrene resin, epoxy resin, and polyamide resin are used in a wide range of fields such as mechanical parts, electrical parts, and automobile parts by taking advantage of their excellent physical properties. There is. On the other hand, since these resins are flammable in nature, safety against flames, that is, high flame retardancy is required in addition to the balance of general chemical and physical properties in order to use them for the above purposes. Often done.

There are various methods for exhibiting flame retardancy, but usually, a flame retardant of a halogen compound and a flame retardant aid such as an antimony compound are added. However, since such a flame retardant generally generates corrosive gas during processing or combustion, there is a problem such as an increase in man-hours due to maintenance of the mold during molding processing. Further, in the future, there is a concern about the influence on the environment at the time of product disposal, and a flame retardant resin composition containing no halogen-based flame retardant is desired.

As a method for making a flame retardant without using a halogen-based flame retardant, it is widely known to add a metal hydrate such as aluminum hydroxide or magnesium hydroxide. However, in order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above metal hydrate, which has a drawback that the original characteristics of the resin are lost.

Alternatively, organophosphorus compounds have been widely used and much research has been done. Typical examples of such compounds include triphenylphosphine. However, the addition of triphenylphosphine greatly reduces the heat resistance of the composition, and since triphenylphosphine is highly volatile, a large amount of gas is generated during extrusion and molding, which causes a problem in handleability. .. Further, this compound has a problem that when the resin is heated to a high temperature, at least a part thereof is volatilized or lost from the resin due to bleeding or the like.

In particular, in the flame retardancy of heat-resistant polyamides such as semi-aromatic polyamides, there are some examples of using specific organic phosphorus compounds (Patent Document 1), but since heat-resistant polyamides have a high processing temperature due to their high melting point, organic phosphorus is used. When a compound is used, the above-mentioned problems such as gas generation, handleability, and bleeding tend to become remarkable, and it is difficult to make it highly flame-retardant with a small blending amount. Inorganic phosphorus compounds such as phosphinic acid metal salts are used to make heat-resistant polyamide flame-retardant, but during melting, metal parts such as extruder screws and dies and molding machine screws and dies are violently damaged. There was a metal corrosive problem of wear.

Japanese Unexamined Patent Publication No. 2012-67172

An object of the present invention is to provide a flame-retardant resin composition capable of achieving a high degree of flame retardancy even in a thermoplastic resin having particularly high heat resistance, and a molded product comprising the flame-retardant resin composition.

As a result of diligent research, the present inventors have found that a pentaerythritol diphosphonate compound containing a specific structure has high heat resistance, and by using it, the above object can be achieved, and the present invention is completed. I came to do.
That is, according to the present invention, the subject of the invention is achieved by the following.

1. 1. A flame-retardant resin composition containing (A) a thermoplastic resin (component A) and (B) a pentaerythritol diphosphonate compound (component B) represented by the following formula (1), with respect to 100 parts by weight of the component A. A flame-retardant resin composition comprising 1 to 50 parts by weight of the B component.

(In formula (1), R ¹ , R ² , R ³ and R ⁴ may be independent or the same, respectively, and may be a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or carbon. Saturated or unsaturated hydrocarbon groups of number 1 to 20. R ⁵ and R ⁶ may be independent or the same, respectively, and are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms and carbon atoms. It is a substituted or unsubstituted aryloxy group of 6 to 20, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.)

2. 2. The flame-retardant resin composition according to item 1 above, wherein the pentaerythritol diphosphonate compound (component B) has a 5% weight loss temperature of 370 ° C. or higher as determined by thermogravimetric analysis (TGA).
3. 3. The flame-retardant resin composition according to the above item 1 or 2, wherein the pentaerythritol diphosphonate compound (component B) is a compound represented by the following formula (2).

4. The flame-retardant resin composition according to any one of the above items 1 to 3, wherein the thermoplastic resin (component A) is a semi-aromatic polyamide.
5. A molded product formed from the flame-retardant resin composition according to any one of the above items 1 to 4.

According to the present invention, by using a pentaerythritol diphosphonate compound containing a specific structure, it is possible to impart a high degree of flame retardancy even to a thermoplastic resin, particularly a resin having high heat resistance such as a heat resistant polyamide.

Hereinafter, the present invention will be described in detail.

The flame-retardant resin composition of the present invention contains (A) a thermoplastic resin (component A) and (B) a pentaerythritol diphosphonate compound (component B) represented by the above formula (1). The component A is the main component of the resin composition for molding, and the component B is a component for imparting flame retardancy. As for the mixing ratio, the B component is 1 to 50 parts by weight, preferably 1.5 to 40 parts by weight, more preferably 2 to 30 parts by weight, and further preferably 3 to 20 parts by weight with respect to 100 parts by weight of the A component. Preferably, 4 to 15 parts by weight is particularly preferable, and 5 to 10 parts by weight is most preferable.

Examples of the thermoplastic resin used as the component A of the present invention include chlorinated polyethylene, polyethylene, polypropylene, polybutadiene, polystyrene, impact resistant polystyrene, AS resin, ABS resin, polyvinyl chloride, polyphenylene ether, polymethyl methacrylate, and polyamide. Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and other polyesters, polycarbonate, polyphenylene sulfide, polysulfone, polyether sulfone, polyimide, polyether ether ketone, polyarylate, polyether nitrile, polythioether sulfone, poly Examples thereof include benzimidazole, polycarbonate, liquid crystal resin, and composite plastic. The above resin may be used alone or in combination of two or more. Of these, polyamides and polyesters are preferable, and semi-aromatic polyamides are particularly preferable.

In the present invention, the pentaerythritol diphosphonate compound (component B) represented by the following formula (1) is used as a flame retardant.

In formula (1), R ¹ , R ² , R ³ and R ⁴ may be independent or the same, respectively, and may be a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a carbon number of carbon atoms. 1 to 20 saturated or unsaturated hydrocarbon groups.

R ¹ , R ² , R ³ and R ⁴ are hydrogen atom, methyl group, ethyl group, various propyl group, various butyl group, various pentyl group, propenyl group, phenyl group, various toluyl group, various xylyl group, various cumenyl group. , Di-t-butylphenyl group, biphenyl group, naphthyl group are preferable, hydrogen atom, methyl group, ethyl group, various propyl groups, various butyl groups, various pentyl groups, propenyl group, phenyl group and various toluyl groups are more preferable. , Hydrogen atom, methyl group, ethyl group, phenyl group are more preferable, and hydrogen atom is particularly preferable.

In formula (1), R ⁵ and R ⁶ may be independent or the same, respectively, and are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms. It is an oxy group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

R ⁵ and R ⁶ are hydrogen atom, methyl group, ethyl group, various propyl group, various butyl group, various pentyl group, methoxy group, ethoxy group, various propyloxy group, various butoxy group, phenyl group, various xylyl group, Various toluyl groups, di-t-butylphenyl groups, various cumenyl groups, biphenyl groups, naphthyl groups, phenoxy groups, various xyloxy groups, various toluoxy groups, di-t-butylphenoxy groups, naphthoxy groups are preferable, and phenyl groups and various types. A xylyl group, various toluyl groups, a phenoxy group and various xyloxy groups are more preferable, a phenyl group, various xylyl groups and a phenoxy group are more preferable, and a phenyl group is particularly preferable.

Specifically, as the pentaerythritol diphosphonate compound represented by the formula (1),
3,9-bis (2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9 -Bis (2-((oxo) bis (2-methylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3 , 9-Bis (2-((oxo) bis (3-methylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane , 3,9-bis (2-((oxo) bis (4-methylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ] Undecane, 3,9-bis (2-((oxo) bis (2,4-dimethylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, 3,9-bis (2-((oxo) bis (2,6-dimethylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3 , 9-Diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (3,5-dimethylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10 -Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,4,6-trimethylphenyl) phosphino) ethyl) -3,9-dioxo-2 , 4,8,10-Tetraoxa-3,9-Diphosphaspiro [5.5] Undecane,

3,9-Bis (2-((oxo) bis (2-sec-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5. 5] Undecane, 3,9-bis (2-((oxo) bis (4-sec-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,4-di-sec-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8, 10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,6-di-sec-butylphenyl) phosphino) ethyl) -3,9- Dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,4,6-tri-sec-butylphenyl) ) Phenyl) Ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane,

3,9-Bis (2-((oxo) bis (2-tert-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5. 5] Undecane, 3,9-bis (2-((oxo) bis (4-tert-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,4-di-tert-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8, 10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,6-di-tert-butylphenyl) phosphino) ethyl) -3,9- Dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) bis (2,4,6-tri-tert-butylphenyl) ) Phenyl) Ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane,

3,9-bis (2-((oxo) bis (4-biphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane , 3,9-bis (2-((oxo) bis (1-naphthyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, 3,9-bis (2-((oxo) bis (2-naphthyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ] Undecane, 3,9-bis (2-((oxo) bis (1-anthryl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5. 5] Undecane, 3,9-bis (2-((oxo) bis (2-anthryl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5] .5] Undecane, 3,9-bis (2-((oxo) bis (9-anthryl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5] Undecane,

3,9-bis (2-((oxo) diphenoxyphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3, 9-Bis (2-((oxo) bis (2,6-dimethylphenoxy) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, 3,9-bis (2-((oxo) bis (2,6-di-tert-butylphenoxy) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3, 9-Diphosphaspiro [5.5] Undecane,

3,9-Bis (1-methyl-2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane , 3,9-bis (2-((oxo) diphenylphosphino) propyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3, 9-Bis (1-phenyl-2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3 , 9-Bis (2-phenyl-2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane,

3- (2-((oxo) diphenylphosphino) ethyl) -9- (2-((oxo) bis (2,6-dimethylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8 , 10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-(2-((oxo) diphenylphosphino) ethyl) -9-(2-((oxo) bis (2,6-di-) tert-butylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-(2-((oxo) diphenylphosphino) ) Ethyl) -9- (1-Methyl-2-((oxo) diphenylphosphino) ethyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5] Undecane, 3- (2-((oxo) bis (2,6-dimethylphenyl) phosphino) ethyl) -9- (1-methyl-2-((oxo) diphenylphosphino) ethyl) phosphino) Ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-(2-((oxo) bis (2,6-di-tert-) Butylphenyl) phosphino) ethyl) -9- (1-methyl-2-((oxo) diphenylphosphino) ethyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3, 9-Diphosphaspiro [5.5] undecane, 3- (1-phenyl-2-((oxo) diphenylphosphino) ethyl) -9- (1-methyl-2-((oxo) diphenylphosphino) ethyl) phosphino ) Ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3- (1-phenyl-2-((oxo) diphenylphosphino) ethyl ) -9- (2-((oxo) bis (2,6-dimethylphenyl) phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ] Undecane, 3- (1-phenyl-2-((oxo) diphenylphosphino) ethyl) -9- (2-((oxo) bis (2,6-di-tert-butylphenyl) phosphino) ethyl)- 3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane,

3,9-bis (2-((oxo) dimethylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9 -Bis (2-((oxo) diethylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ( 2-((oxo) diisopropylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-( (Oxo) dimethoxyphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo)) Diethoxyphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) diisopropyloxy) Phosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane can be mentioned.

Among them, 3,9-bis (2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2-((oxo) diphenoxyphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3, 9-bis (1-methyl-2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3 , 9-Bis (2-((oxo) diphenylphosphino) propyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9- Bis (1-phenyl-2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane is preferred.

In particular, the pentaerythritol diphosphonate compound represented by the following formula (2) is preferable.

There are various production methods for such compounds. For example, pentaerythritol is reacted with phosphorus trichloride, and then a hydroxyl group-containing compound such as water, alcohol, or carboxylic acid is allowed to act as a hydrogen-introducing agent to cause pentaerythritol. It can be obtained by obtaining a dihydrophosphonate and further reacting a vinyl phosphorus compound under a transition metal catalyst, but it may be produced by another method.

The pentaerythritol diphosphonate compound of the present invention preferably has a 5% weight loss temperature determined by thermogravimetric analysis (TGA) of 370 ° C. or higher, and more preferably 380 ° C. or higher. When the 5% weight loss temperature is 370 ° C. or higher, thermal decomposition is unlikely to proceed during extrusion and molding, and when used as a flame retardant for a resin having a high processing temperature, high flame retardancy should be imparted. Can be done.

In general, inorganic phosphorus compounds such as red phosphorus and phosphinic acid metal salts are used as phosphorus-based flame retardants with high heat resistance, but these generate phosphine gas during melt processing and cause metal corrosion that violently wears metal parts. I have a sexual problem. The pentaerythritol diphosphonate compound of the present invention is an organic phosphorus compound and does not cause metal corrosion.

The flame retardant resin composition of the present invention contains, in addition to the pentaerythritol diphosphonate compound (component B), a flame retardant other than the component B, a flame retardant aid, and fluorine, as long as the effects of the present invention are not impaired. Naturally, resin or other additives are used to reduce the proportion of B component used, improve the flame retardancy of the molded product, improve the physical properties of the molded product, improve the chemical properties of the molded product, or for other purposes. Can be blended.

As the flame retardant other than the B component, for example, another phosphorus or a phosphorus-based flame retardant (C component) can be used. Examples of the C component include the following (C-1) to (C-7). (C-1): Red phosphorus (C-2): Phosphinic acid metal salt represented by the following general formula (C-2)

(C-3): Diphosphinic acid metal salt represented by the following general formula (C-3)

(C-4): Triaryl phosphate represented by the following general formula (C-4)

(C-5): Condensed phosphoric acid ester represented by the following general formula (C-5)

(C-6): Condensed phosphoric acid ester represented by the following general formula (C-6)

(C-7): Organic phosphorus compound represented by the following general formula (C-7)

In the formulas (C-2) and (C-3), ^R7 and R8 may be independent or the ^same , respectively, and may be an alkyl group or a branched chain having 1 to 16 carbon atoms. It is an aryl group of 6 to 15, preferably a linear or branched alkyl group or a phenyl group having 1 to 8 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-. Butyl group, tert-butyl group, n-pentyl group, n-octyl group and phenyl group. R ⁷ and R ⁸ may form a ring with each other.

R ⁹ is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group having 6 to 10 carbon atoms, or an alkyl arylene group having 6 to 10 carbon atoms.

M is an alkaline earth metal, an alkali metal, zinc, aluminum, iron, or boron, preferably calcium, aluminum, magnesium, zinc, and more preferably aluminum.

m represents the valence of the metal ion and is an integer of 1 to 3. a represents the number of metal ions, b represents the number of diphosphinic acid ions, and a and b are integers satisfying the relational expression of 2 × b = m × a.

^Q1 to ^Q4 in the formulas (C-4) to (C-6) may be the same or different from each other, and may be an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms. be. Specific examples of this aryl group include a phenyl group, a naphthyl group, or an anthryl group. These aryl groups may have 1 to 5, preferably 1 to 3 substituents, and the substituents include (i) a methyl group, an ethyl group, a propyl group, an isopropyl group and n-butyl. An alkyl group having 1 to 12 carbon atoms such as a group, a sec-butyl group, a tert-butyl group, a neopentyl group and a nonyl group, preferably an alkyl group having 1 to 9 carbon atoms, (ii) a methoxy group, an ethoxy group and a propoxy group. , Butoxy group and alkyloxy group having 1 to 12 carbon atoms such as pentoxy group, preferably alkyloxy group having 1 to 9 carbon atoms, (iii) methylthio group, ethylthio group, propylthio group, butylthio group and pentylthio group. An alkylthio group having a number of 1 to 12, preferably an alkylthio group having 1 to 9 carbon atoms and a group represented by the formula (iv) Ar ³ -W1- (where W ¹ is -O-, -S- or 1 carbon number). -8, preferably an alkylene group having 1 to 4 carbon atoms, and Ar ³ indicates an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms).

In formulas (C-5) and (C-6), Ar ¹ and Ar ² may be the same or different when both are present (in the case of C-6), and are allylenes having 6 to 15 carbon atoms. A group, preferably an arylene group having 6 to 10 carbon atoms is shown. Specific examples include a phenylene group or a naphthylene group. This arylene group may have 1 to 4, preferably 1 to 2 substituents. Such substituents include (i) an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group, and (ii) benzyl. An aralkyl group having 7 to 20 carbon atoms such as a group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a cumyl group, and a group represented by the formula (iii) Q5 ^{- W2- (} where W2 is -O- or -S-, where Q5 represents an alkyl group having 1 to ⁴ carbon atoms, preferably 1 to 3 carbon atoms or an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms) and (iv) a phenyl group. Examples thereof include an aryl group having 6 to 15 carbon atoms.

In the formulas (C-5) and (C-6), n represents an integer of 1 to 5, preferably an integer of 1 to 3, and is particularly preferably 1.

In formula (C-6), Z is a single bond or group that binds Ar ¹ and Ar ² , and -Ar ¹ -Z-Ar ^2- is a residue usually derived from bisphenol. Thus Z represents a single bond, —O—, —CO—, —S—, _—SO2- or an alkylene group having 1-3 carbon atoms, preferably single bond, —O—, or isopropylidene.

The aromatic ring of the formula (C-7) may have 1 to 4, preferably 1 to 3 substituents, and the substituents include (i) a methyl group, an ethyl group, and a propyl group. An alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 9 carbon atoms, such as a group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a neopentyl group and a nonyl group, (ii). Alkyloxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group, preferably alkyloxy group having 1 to 9 carbon atoms, (iii) methylthio group, ethylthio group, propylthio group, An alkylthio group having 1 to 12 carbon atoms such as a butylthio group and a pentylthio group, preferably an alkylthio group having 1 to 9 carbon atoms and a group represented by the formula (iv) Ar ³ -W1- (where W ¹ is -O-). , —S— or an alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and Ar ³ indicates an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms).

Even phosphorus compounds other than the phosphorus or phosphorus compounds of (C-1) to (C-7) described above can be used in combination with the B component.

When the phosphorus or phosphorus compound of (C-1) to (C-7) is blended in the resin composition, the ratio thereof is preferably 1 to 100 parts by weight per 100 parts by weight of the organic phosphorus compound (B component). More preferably, the range is 5 to 80 parts by weight, and particularly preferably 10 to 60 parts by weight. Among the phosphorus or phosphorus compounds of (C-1) to (C-7), the phosphorus compounds of (C-4) to (C-7) are preferable.

As a flame retardant aid, the resin composition of the present invention can be further blended with Biscmil (component D) represented by the following chemical formula.

The aromatic ring of this biscumil compound may preferably have 1 to 5 substituents, more preferably 1 to 3 substituents, and the substituents include (i) a methyl group and an ethyl group. , An alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 9 carbon atoms, such as a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a neopentyl group and a nonyl group. ii) Alkyloxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group, preferably alkyloxy groups having 1 to 9 carbon atoms, (iii) methylthio group, ethylthio group, propylthio. An alkylthio group having 1 to 12 carbon atoms such as a group, a butylthio group and a pentylthio group, preferably an alkylthio group having 1 to 9 carbon atoms and a group represented by the formula (iv) Ar ³ − W ¹ − (where W ¹ is). —O—, —S— or an alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, Ar ³ represents an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms). Can be mentioned.

When this biscumill (component D) is blended in the polyamide resin composition, the ratio thereof is preferably 0.01 to 3 parts by weight, more preferably 0.02 with respect to 100 parts by weight of the thermoplastic resin (component A). It is ~ 2 parts by weight, particularly preferably 0.03 ~ 1 part by weight. It is presumed that the flame-retardant effect of blending this biscmill in the above ratio is due to the generation of radicals, and as a result, the level of flame-retardant property is improved.

Further known flame retardant aids can be added to the resin composition of the present invention. Examples of the flame retardant aid include silicone oil. The silicone oil has a polydiorganosiloxane as a skeleton, preferably polydiphenylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane, or any copolymer or mixture thereof, and polydimethylsiloxane is preferably used. .. Its viscosity is preferably 0.8 to 5000 cmpoise (25 ° C.), more preferably 10 to 1000 cmpoise (25 ° C.), still more preferably 50 to 500 cmpoise (25 ° C.), and those having such a viscosity range are difficult. It has excellent flammability and is preferable. The blending amount of the silicone oil is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (component A).

Examples of other flame retardant aids include nitrogen-containing compounds. Among the nitrogen-containing compounds, a triazine group-containing compound is particularly preferable, and a melamine salt-based compound is more preferable.

Further, the resin composition of the present invention can also contain various flame-retardant improving agents. Examples of the flame-retardant improver that can be blended in the resin composition of the present invention include thermosetting resins typified by phenol resins and epoxy resins.

The phenol resin used as the flame retardant improver is arbitrary as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak type, resole type and heat reaction type resins, and resins modified thereto. Be done. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Of these, phenol novolac resin, which does not contain a curing agent and is non-reactive, is preferable in terms of flame retardancy, impact resistance, and economy. The shape is not particularly limited, and any of crushed products, granules, flakes, powders, needles, liquids and the like can be used. The above-mentioned phenol resin can be used as one kind or a mixture of two or more kinds as needed.

The phenol resin is not particularly limited, and a commercially available phenol resin can be used. For example, in the case of novolak-type phenol resin, the molar ratio of phenols to aldehydes is charged in the reaction vessel so as to be 1: 0.7 to 1: 0.9, and further, oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid and the like are charged. After adding the catalyst of the above, heating and reflux reaction are carried out. It is obtained by vacuum dehydration or static dehydration to remove the generated water, and further removing the remaining water and unreacted phenols. By using a plurality of raw material components for these resins, a cocondensation phenol resin can be obtained, and this can also be used in the same manner.

In the case of a resol-type phenol resin, the molar ratio of phenols to aldehydes is 1: 1 to 1: 2, and the reaction tank is charged with a catalyst such as sodium hydroxide, aqueous ammonia, and other basic substances. Can be obtained by performing the same operation as that of the novolak type phenol resin.

Here, the phenols are phenol, o-cresol, m-cresol, p-cresol, timol, p-tert-butylphenol, tert-butylcatechol, catechol, isooigenol, o-methoxyphenol, 4,4'-dihydroxy. Examples thereof include phenylpropane, isoamyl sartylate, benzyl sultylate, methyl sulcylate, 2,6-di-tert-butyl-p-cresol and the like. These phenols can be used as one kind or a mixture of two or more kinds as needed. On the other hand, examples of aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can also be used as one kind or a mixture of two or more kinds as needed.

The molecular weight of the phenol resin is also not particularly limited, but those having a number average molecular weight of 200 to 2,000, more preferably 400 to 1,500 are mechanical properties, molding processability, and economic efficiency. Excellent and preferable.

The epoxy resin used as a flame retardant improver is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy. Examples thereof include a resin, a naphthalene type epoxy resin, and a biphenol type epoxy resin, but the present invention is not particularly limited thereto. These epoxy resins are not limited to only one type in their use, and may be used in combination of two or more types or various modified ones.

When the flame-retardant improved resin (thermosetting resin) is blended, the ratio thereof is preferably 0.01 to 45 parts by weight, more preferably 0.1 with respect to 100 parts by weight of the thermoplastic resin (component A). It is about 40 parts by weight, particularly preferably 0.5 to 35 parts by weight.

A fluorine-containing resin can be further added to the flame-retardant resin composition of the present invention as a dripping inhibitor. The flame retardancy of the molded product is improved by blending the fluorine-containing resin. In particular, dripping in the combustion test of the molded product is suppressed.

The fluorine-containing resin used as the dripping inhibitor is not particularly limited as long as it has a fibril-forming ability, and is, for example, tetrafluoroethylene, trifluoroethylene, vinylfluoride, vinylidenefluoride, hexafluoropropylene. Fluorine-containing monomers alone or copolymers such as. In particular, polytetrafluoroethylene having a fibril-forming ability is preferable. As the polytetrafluoroethylene having a fibril-forming ability, it is a powder obtained by emulsion polymerization of tetrafluoroethylene and dried by coagulation (so-called polytetrafluoroethylene fine powder), and is classified into type 3 in the ASTM standard. Things). Alternatively, an aqueous dispersion (so-called polytetrafluoroethylene dispersion) produced by adding a surfactant to the latex and concentrating and stabilizing it can be mentioned.

The molecular weight of polytetrafluoroethylene having such a fibril-forming ability is preferably 1 million to 10 million, more preferably 2 million to 9 million in terms of the number average molecular weight obtained from the standard specific gravity.

Further, the polytetrafluoroethylene having such a fibril-forming ability preferably has a primary particle size in the range of 0.05 to 1.0 μm, and more preferably 0.1 to 0.5 μm. When a fine powder is used, a secondary particle diameter of 1 to 1,000 μm can be used, and more preferably 10 to 500 μm can be used.

Such polytetrafluoroethylene has a melt dripping prevention performance at the time of a combustion test of a test piece in a vertical combustion test of UL standard, and specifically, as a polytetrafluoroethylene having such a fibril forming ability, for example, Mitsui-Dupont. Fluorochemical Co., Ltd. Teflon® 6J and Teflon® 30J, Daikin Chemical Industry Co., Ltd. Polyflon MPA FA-500, Polyflon F-201L and Polyflon D-1, and Asahi Icy Eye Fluoro CD076 manufactured by Polymers Co., Ltd. and the like can be mentioned.

As the polytetrafluoroethylene, those which have been subjected to various treatments in order to prevent secondary aggregation are more preferably used in the fin powder. Examples of such treatment include calcination of the surface of polytetrafluoroethylene. Further, as such a treatment, the surface of polytetrafluoroethylene having a fibril-forming ability may be coated with polytetrafluoroethylene having a non-fibril-forming ability. More preferred in the present invention is polytetrafluoroethylene treated with the latter. This is because in the former case, the target fibril forming ability tends to decrease. In such a case, polytetrafluoroethylene having a fibril-forming ability is preferably in the range of 70 to 95% by weight of the total amount. The molecular weight of the non-fibril-forming polytetrafluoroethylene is preferably 10,000 to 1,000,000, more preferably 10,000 to 800,000 in terms of the number average molecular weight obtained from the standard specific gravity.

As the polytetrafluoroethylene (hereinafter, may be referred to as PTFE), in addition to the solid form as described above, an aqueous dispersion form can also be used.

As the polytetrafluoroethylene, an aqueous emulsion and a dispersion form can be used in addition to the usual solid form, but the solid state is particularly preferable because the dispersant component tends to adversely affect the moist heat resistance. Can be used.

Further, the polytetrafluoroethylene having such a fibril-forming ability improves the dispersibility in the resin, and in order to obtain a better appearance and mechanical properties, the emulsion of the polytetrafluoroethylene and the emulsion of the vinyl polymer are combined. Aggregate mixtures can also be mentioned as preferred forms.

Here, the vinyl-based polymer includes a block copolymer composed of polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, AAS resin, polymethyl (meth) acrylate, styrene and butadiene, and water thereof. Copolymers, block copolymers composed of styrene and isoprene, and hydrogenated copolymers thereof, acrylonitrile-butadiene copolymers, ethylene-propylene random copolymers and block copolymers, and ethylene-butene random copolymers. Polymers and block copolymers, copolymers of ethylene and α-olefins, copolymers of ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylic acid esters such as butyl acrylate-butadiene-butadiene co-weight. Combined, rubber-like polymers such as polyalkyl (meth) acrylate, composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, and vinyl-based monomers such as styrene, acrylonitrile, and polyalkylmethacrylate are added to the composite rubber. Examples thereof include a grafted copolymer.

In order to prepare such an agglomerated mixture, an aqueous emulsion of the vinyl-based polymer having an average particle size of 0.01 to 1 μm, particularly 0.05 to 0.5 μm, is subjected to an average particle size of 0.05 to 10 μm, particularly 0. Mix with an aqueous emulsion of polytetrafluoroethylene having a size of 0.05-1.0 μm. Such a polytetrafluoroethylene emulsion can be obtained by polymerizing polytetrafluoroethylene by emulsion polymerization using a fluorine-containing surfactant. At the time of such emulsion polymerization, it is also possible to copolymerize other copolymer components such as hexafluoropropylene with 10% by weight or less of the total polytetrafluoroethylene.

When obtaining such an agglomerated mixture, a suitable polytetrafluoroethylene emulsion usually has a solid content of 40 to 70% by weight, particularly 50 to 65% by weight, and an emulsion of a vinyl polymer has a solid content of 25 to 50% by weight. Those having a solid content of 60% by weight, particularly 30 to 45% by weight, are used. Further, the proportion of polytetrafluoroethylene in the agglomerated mixture is preferably 1 to 80% by weight, particularly 1 to 60% by weight, based on 100% by weight of the total of the vinyl-based polymer used in the agglomerated mixture. A production method in which the above emulsion is mixed, mixed by stirring, put into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salted out and solidified to be separated and recovered can be preferably mentioned. Alternatively, a method of recovering the stirred mixed emulsion by a method such as spray drying or freeze-drying can be mentioned.

Further, various forms of agglomerated mixture of a polytetrafluoroethylene emulsion having a fibril-forming ability and a vinyl-based polymer emulsion can be used, for example, a vinyl-based polymer is formed around the polytetrafluoroethylene particles. Examples thereof include a form in which polytetrafluoroethylene surrounds a vinyl-based polymer, a form in which several particles are aggregated with respect to one particle, and the like.

Further, a vinyl-based polymer of the same or another type graft-polymerized on the outer layer of the aggregated mixture can also be used. Preferred examples of the vinyl-based monomer include styrene, α-methylstyrene, methyl methacrylate, cyclohexyl acrylate, dodecyl methacrylate, dodecyl acrylate, acrylonitrile, and -2-ethylhexyl acrylate. Can be used alone or copolymerized.

As commercial products of the aggregated mixture of the above emulsion of polytetrafluoroethylene having the ability to form fibrils and the emulsion of vinyl polymer, Metabrene "A3000" from Mitsubishi Rayon Co., Ltd. and "BLENDEX 449" from GE Specialty Chemicals Co., Ltd. Can be mentioned as a typical example.

When the fluorine-containing resin is blended, the ratio is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin (component A). If it is 0.01 parts by weight or more, sufficient melt dripping prevention performance can be easily obtained, and if it is 10 parts by weight or less, appearance defects and dispersion defects are less likely to occur, and it is economically advantageous.

The flame-retardant resin composition of the present invention contains various additives such as antioxidants, UV absorbers, deterioration inhibitors such as light-resistant stabilizers, lubricants, antistatic agents, mold release agents, plasticizers, and glass. Reinforcing fibers such as fibers and carbon fibers, fillers such as talc, mica and wallastonite, and colorants such as pigments may be added. The amount of the additive used can be appropriately selected according to the type of the additive within a range that does not impair heat resistance, impact resistance, mechanical strength, and the like.

The flame-retardant resin composition of the present invention has extremely high flame-retardant performance, and is a material for molding various molded products such as home appliance parts, electric / electronic parts, automobile parts, mechanical / mechanical parts, and cosmetic containers. It is useful as. Specifically, breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power outlets, coil bobbins, connectors, relay cases, fuse cases, flyback transformer parts, focus block parts, distributor caps, harness connectors, etc. Can be suitably used for. In addition, housings, casings or chassis that are becoming thinner, such as housings for electronic and electrical products (eg telephones, personal computers, printers, fax machines, copiers, video decks, home appliances and OA equipment such as audio equipment, or their parts). Useful for casings or chassis. It is also useful as a housing for printers, fixing unit parts, and mechanical / mechanical parts for home appliances / OA products such as fax machines, which are required to have particularly excellent heat resistance and flame retardancy.

Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples. The evaluation was performed by the following method.

(1) 5% weight reduction temperature The temperature was measured at a heating rate of 20 ° C./min by a DTG-60A (thermogravimetric measuring device) manufactured by Shimadzu Corporation.

(2) Flame Retardant Each component shown in Table 2 was blended in the amount (part by weight) shown in Table 2 and pelletized with a 15 mmΦ twin-screw extruder (manufactured by Technobel, KZW15). The obtained pellets were dried in a hot air dryer at 120 ° C. for 5 hours. The pellet was molded into a 12.5 mm × 125 mm × 1.6 mm (1/16 inch) test piece by an injection molding machine (Japan Steel Works, Ltd., J75EEIII).
The combustion time after indirect flame was applied to the lower end of the test piece with a gas burner for 10 seconds was measured, and when the combustion stopped within 30 seconds, the combustion time was measured by indirect flame for another 10 seconds. Five of these measurements were carried out and comparative evaluations were made regarding the total combustion time and maximum combustion time for all flame contact.

<Thermoplastic resin (component A)>
A-1: Nylon 9T (manufactured by Kuraray Co., Ltd., trade name Genestar N1000A)
A-2: Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd., trade name 500FP EF202X)
<Phosphorus compound (B component)>
B-1: 3,9-bis (2-((oxo) diphenylphosphino) ethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (Made by Katayama Chemical Industry Co., Ltd.)
B-2: 1,3-phenylenebis (dixylenyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200)
B-3: Phosphinate compound (manufactured by Clariant, trade name Exolit OP1240)
The 5% weight loss temperature of each phosphorus compound is shown in Table 1 below.

<Examples 1 to 5, Comparative Examples 1 to 7>
Each component shown in Table 2 is blended in the amount (part by weight) shown in Table 2, pelletized with a 15 mmΦ twin-screw extruder (Technobel, KZW15), and the dried pellets are injected into an injection molding machine (Japan Steel Works, Ltd.). , J75EEIII) and evaluated. The results are shown in Table 2.

By using the pentaerythritol diphosphonate compound of the present invention, a resin composition having a short burning time and excellent flame retardancy was obtained.

The polycarbonate resin composition of the present invention has extremely high flame retardant performance and is useful as a material for molding various molded products such as home appliance parts, electric / electronic parts, automobile parts, mechanical / mechanical parts, and cosmetic containers. Is.

Claims (5)

A flame-retardant resin composition containing (A) a thermoplastic resin (component A) and (B) a pentaerythritol diphosphonate compound (component B) represented by the following formula (1), with respect to 100 parts by weight of the component A. A flame-retardant resin composition comprising 1 to 50 parts by weight of the B component.

(In formula (1), R ¹ , R ² , R ³ and R ⁴ may be independent or the same, respectively, and may be a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or carbon. Saturated or unsaturated hydrocarbon groups of number 1 to 20. R ⁵ and R ⁶ may be independent or the same, respectively, and are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms and carbon atoms. It is a substituted or unsubstituted aryloxy group of 6 to 20, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.) The flame-retardant resin composition according to claim 1, wherein the pentaerythritol diphosphonate compound (component B) has a 5% weight loss temperature determined by thermogravimetric analysis (TGA) of 370 ° C. or higher. The flame-retardant resin composition according to claim 1 or 2, wherein the pentaerythritol diphosphonate compound (component B) is a compound represented by the following formula (2).

The flame-retardant resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (component A) is a semi-aromatic polyamide. A molded product formed from the flame-retardant resin composition according to any one of claims 1 to 4.