JP2021138664A - Organic phosphorus compound, thermoplastic resin composition, and electronic apparatus - Google Patents

Abstract

To provide an organic phosphorus compound that has high compatibility with a polyolefin resin and expresses flame retardancy stably for a long time in a molding of a thermoplastic resin composition comprising the polyolefin resin and the organic phosphorus compound.SOLUTION: An organic phosphorus compound has a structure of general formula (1) (in the formula (1), R1 is H, an optionally substituted alkyl group or alkoxy group, R2 and R3 independently represent an optionally substituted alkyl group, aryl group or aralkyl group, R2 and R3 may be the same or different. X is a divalent linking group).SELECTED DRAWING: None

Description

The present invention relates to organophosphorus compounds, thermoplastic resin compositions and electronic devices. More specifically, the present invention provides an organic phosphorus compound that has high compatibility with a polyolefin resin and exhibits stable flame retardancy for a long period of time in a molded product of a thermoplastic resin composition containing the polyolefin resin together with the polyolefin resin. The present invention relates to a thermoplastic resin composition containing a polyolefin resin and the organic phosphorus compound, and an electronic device using parts manufactured by using the thermoplastic resin composition.

As the resin composition used as the interior / exterior material of electronic devices including copiers and the like, a thermoplastic resin composition that is easy to mold and secures flame retardancy is used. In order to ensure flame retardancy, it is common to add a flame retardant as an additive to the resin.

Organic phosphorus compounds, metal hydroxides, and the like are generally used as flame retardants, but polyolefin resins, which are easy to mold, have a low oxygen index, which is one of the flame retardant indicators. It was a problem to secure a predetermined flame retardancy. In addition, since the resin has high hydrophobicity, it has poor compatibility with flame retardants having many polar structures. In particular, organic phosphoric acid esters having a low melting point cause bleed-out to the resin surface during molding, and the resin composition. In the molding process of the above, there has been a problem of molding variation, particularly fluctuation of strength and physical properties.

Further, as one of the methods for improving the flame retardancy of a flame retardant using an organic phosphoric acid compound, a method of using a hindered amine-based antioxidant in combination as an additive has been presented (for example, Patent Documents 1 to 3). See).

Hindered amine-based antioxidants are effective means for improving flame retardancy as radical trapping agents because they suppress thermal decomposition and combustion reactions of resins. In order to measure it and to exert its effect as a light stabilizer, there has been a problem that the flame retardancy decreases after long-term exposure to light. Further, even when the organic phosphoric acid compound and the hindered amine-based antioxidant are used in combination, the problems of bleed-out and fluctuation of strength physical properties have not been solved.

JP-A-2018-30939 Japanese Unexamined Patent Publication No. 2001-348724 Japanese Unexamined Patent Publication No. 2004-83913

The present invention has been made in view of the above problems and situations, and the problem to be solved thereof is that it has high compatibility with polyolefin-based resins and is long in molded products of thermoplastic resin compositions containing the polyolefin-based resins. It is to provide an organic phosphorus compound which exhibits flame retardancy stably for a period of time. In addition, a thermoplastic resin composition containing a polyolefin-based resin as a main component, which can produce a molded product that stably exhibits flame retardancy even after long-term use by containing the above-mentioned organic phosphorus compound, and a thermoplastic resin composition using the same. The purpose is to provide an electronic device having a manufactured molded product.

In order to solve the above problems, the present inventor newly synthesized an organic phosphorus compound having a specific hindered amine structure bonded to the molecular terminal in the process of examining the cause of the above problem. When this organic phosphorus compound is blended with a thermoplastic resin composition containing a polyolefin resin as a main component, the compatibility with the resin is high, and the molded product obtained from the thermoplastic resin composition is stable for a long period of time. Therefore, they have found that they exhibit flame retardancy, and have reached the present invention.
That is, the above problem according to the present invention is solved by the following means.

1. 1. An organic phosphorus compound having a structure represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group or an alkoxy group which may have a substituent. R ² and R ³ each independently have a substituent. May represent an alkyl group, an aryl group or an alkoxy group. R ² and R ³ may be the same or different. X represents a divalent linking group.)

2. The organic phosphorus compound according to item 1, which has a structure represented by the following general formula (2).

(In the general formula (2), R ⁴ is an aryl group which may have a substituent. X represents a divalent linking group.)

3. 3. A thermoplastic resin composition containing a thermoplastic resin and a flame retardant, wherein the thermoplastic resin contains a polyolefin resin as a main component, and the flame retardant is the organic according to item 1 or 2. A thermoplastic resin composition containing a phosphorus compound.

4. The thermoplastic resin according to Item 3, wherein the content of the organic phosphoric acid compound is in the range of 10 to 40% by mass with respect to the total amount of the thermoplastic resin and the organic phosphoric acid compound. Composition.

5. The thermoplastic resin composition according to item 3 or 4, wherein the polyolefin-based resin is a polypropylene-based resin.

6. An electronic device characterized in that a molded product of the thermoplastic resin composition according to any one of items 3 to 5 is used as a part.

By the above means of the present invention, an organophosphorus compound having high compatibility with a polyolefin-based resin and exhibiting stable flame retardancy for a long period of time in a molded product of a thermoplastic resin composition containing the polyolefin-based resin is provided. can do. In addition, a thermoplastic resin composition containing a polyolefin-based resin as a main component, which can stably produce a molded product that exhibits flame retardancy even after long-term use by containing the above flame retardant, and a thermoplastic resin composition produced using the same. It is possible to provide an electronic device having a molded product.

Although the mechanism of expression or mechanism of action of the effects of the present invention has not been clarified, it is inferred as follows.

The organic phosphorus compound of the present invention has a structure represented by the above general formula (1). Hereinafter, the organic phosphorus compound having the structure represented by the above general formula (1) is also referred to as “organic phosphorus compound (1)”. The organophosphorus compound (1) has a structure in which a part of the organophosphate ester structure is replaced with a hindered amine having a piperidine structure via a connecting chain.

The organophosphorus compound (1) has a highly hydrophobic alkyl group at the piperidine structural site. Due to this structure, the organophosphorus compound (1) has a higher affinity for a polyolefin resin having high hydrophobicity than the conventional organophosphate ester flame retardant. When such an organic phosphorus compound (1) is blended as a flame retardant in a thermoplastic resin composition containing a polyolefin resin as a main component and a molded product is manufactured using the organic phosphorus compound (1), bleed-out of the flame retardant during manufacturing is suppressed. Will be done. As a result, it is considered that the obtained molded product will be a highly flame-retardant molded product to which flame retardancy is sufficiently imparted. Further, it is considered that the strength stability of the obtained molded product can be improved while maintaining a good appearance.

As described above, hindered amine has a radical trapping action, and when used together with a flame retardant composed of an organic phosphorus compound, it acts synergistically with the flame retardant to improve the flame retardant effect. However, it is known that hindered amine also acts as a light-resistant agent and gradually changes its structure in long-term use, resulting in a decrease in flame retardancy.

As described above, the organic phosphorus compound (1) is a compound having both the hindered amine and the organic phosphorus compound structures in one compound. Due to such a structure, the organophosphorus compound (1) has high compatibility with the polyolefin resin, and is formed from a thermoplastic resin composition containing the organophosphorus compound (1) and the polyolefin resin. Increases the stability inside the product. As a result, it is considered that the light resistance stability is increased in the flame retardancy of the obtained molded product.

Schematic perspective view of a large copier as an application example of a molded product of the thermoplastic resin composition of the present invention.

The organic phosphorus compound of the present invention is characterized by having a structure represented by the above general formula (1). This feature is a technical feature common to each of the following embodiments.

As an embodiment of the present invention, from the viewpoint of exhibiting the effect of the present invention, it is preferable that the structure represented by the general formula (1) is a structure represented by the general formula (2).

The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing a thermoplastic resin and a flame retardant, wherein the thermoplastic resin contains a polyolefin resin as a main component, and the flame retardant is the above. It is characterized by containing the organic phosphorus compound of the present invention.

In an embodiment of the present invention, from the viewpoint of exhibiting the effect of the present invention, the content of the organic phosphorus compound is within the range of 10 to 40% by mass with respect to the total amount of the thermoplastic resin and the organic phosphoric acid compound. It is preferable to be in. Further, when the polyolefin-based resin is a polypropylene-based resin, the effect of the present invention is more remarkably exhibited.

The electronic device of the present invention is characterized in that the molded product of the thermoplastic resin composition of the present invention is used as a component.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "~" is used to mean that the numerical values described before and after the value are included as the lower limit value and the upper limit value.

[Organophosphorus compound (1)]
The organophosphorus compound (1) of the present invention has a structure represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group. R ² and R ³ each independently represent an alkyl group, an aryl group or an aralkyl group which may have a substituent. R ² and R ³ may be the same or different. X represents a divalent linking group.

In the general formula (1), when R ¹ is an alkyl group which may have a substituent, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms. .. The alkyl group may be cyclic, branched or linear, and may be a combination thereof. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a hexyl group and an octyl group, and a propyl group, an isopropyl group and a hexyl group are more preferable. In this case, examples of the substituent include an alkoxy group having about 1 to 3 carbon atoms.

In the general formula (1), when R ¹ is an alkoxy group which may have a substituent, the alkyl group constituting the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. ~ 6 is more preferable. The alkyl group may be cyclic, branched or linear, and may be a combination thereof. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a cyclohexyl group and an octyl group, and a methyl group, a propyl group and a cyclohexyl group are preferable, and a cyclohexyl group is particularly preferable. In this case, examples of the substituent include an alkoxy group having about 1 to 3 carbon atoms.

In the general formula (1), R ¹ is preferably an alkoxy group which may have a substituent, and particularly preferably a cyclohexyloxy group.

In the general formula (1), when R ² or R ³ is an alkyl group which may have a substituent, the same embodiment as that of ^{R 1 can be mentioned.} In R ² and ^{R 3,} an ethyl group, a propyl group, a 2-ethylhexyl group is preferred.

In the general formula (1), when R ² or R ³ is an aryl group which may have a substituent, the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and 6 to 12 carbon atoms. 9 is more preferable. In the present specification, the aryl group is a group corresponding to a residue from which a hydrogen atom bonded to any one of carbon atoms forming an aromatic ring has been removed in an aromatic hydrocarbon compound. Examples of the aromatic ring include a benzene ring and a naphthalene ring.

The aryl group includes a case where a hydrogen atom bonded to the aromatic ring is replaced with a hydrocarbon group. Specific examples of the aryl group include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and a biphenyl group, and a phenyl group, a tolyl group and a xsilyl group are preferable. In this case, examples of the substituent include an alkoxy group having about 1 to 3 carbon atoms.

In the general formula (1), when R ² or R ³ is an aralkyl group which may have a substituent, the aryl group preferably has 7 to 13 carbon atoms, more preferably 7 to 9 carbon atoms. In addition, in this specification, an aralkyl group is a group in which an aromatic ring is bonded via an alkylene group. Examples of the aromatic ring include a benzene ring and a naphthalene ring.

The aralkyl group includes a case where a hydrogen atom bonded to the aromatic ring is replaced with a hydrocarbon group. Specific examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, and a diphenylmethyl group. A benzyl group and a 1-phenylethyl group are preferable. In this case, examples of the substituent include an alkoxy group having about 1 to 3 carbon atoms.

In the general formula (1), R ² and R ³ may be the same or different. It is preferable that they are the same from the viewpoint of ease of manufacture. In the general formula (1), ^{it is particularly preferable that R 2} and R ³ are aryl groups which may have a substituent.

In the general formula (1), X is a divalent linking group, specifically, a phenylene group, −O−, an alkylene group having 1 to 3 carbon atoms, an ester bond (−C (= O) O− or -OC (= O)-), amide bond (-NHCO-) and combinations thereof and the like can be mentioned. As the linking group, -O-, an ester bond (-C (= O) O- or -OC (= O)-and -O-phenylene group-O- are preferable. The phenylene group is a 1,4-phenylene group. It is preferable to have.

As the organic phosphorus compound (1), in the general formula (1), R ¹ is a cyclohexyloxy group, R ² and R ³ are aryl groups which may have a substituent, and these are the same. Is preferable. The organic phosphorus compound (1) having such a structure has a structure represented by the following general formula (2). Hereinafter, the organic phosphorus compound (1) having a structure represented by the general formula (2) is also referred to as an organic phosphorus compound (2). Among the organophosphorus compounds (1), the organophosphorus compound (2) has higher compatibility with the polyolefin-based resin, and is stable for a long period of time in a molded product of a thermoplastic resin composition containing the organophosphorus compound (2) together with the polyolefin-based resin. It is an organophosphorus compound having a high flame-retardant effect.

In the general formula (2), R ⁴ is an aryl group which may have a substituent. X represents a divalent linking group. In the general formula (2), the aryl group which may have a substituent represented ^{by R 4 includes a case where R 2} and R ³ are aryl groups which may have a substituent, and a preferred embodiment. Similar aspects can be mentioned including this. As R ⁴ , a phenyl group is particularly preferable.

In the general formula (2), the divalent linking group represented by X is the same as that of X in the general formula (1), and is -O-, an ester bond (-C (= O) O- or -OC (=). O)-and -O-phenylene group-O- are preferable. The phenylene group is preferably a 1,4-phenylene group.

Specific examples of the organic phosphorus compound (1) include organic phosphorus compounds having the structures represented by the following A1 to A5. Hereinafter, the organic phosphorus compound showing the structure represented by A1 is also referred to as an organic phosphorus compound A1. The same applies to the organic phosphorus compounds showing the structures represented by A2 to A5.

Among the organic phosphorus compounds A1 to A5, the organic phosphorus compound A1, the organic phosphorus compound A2, and the organic phosphorus compound A3 are compounds classified into the organic phosphorus compound (2), and the effect of the present invention is more exhibited. It is an organic phosphorus compound.

(Method for producing organic phosphorus compound (1))
The organic phosphorus compound (1) can be produced, for example, by reacting the intermediate (a) and the intermediate (b) as shown in the following reaction formula. The following ^formula, R 1 to R ³ are the same as ^R 1 to R ³ in the general formula (1). ^{Y 1} of the intermediate (a) ^{and Y 2} of the intermediate (b) are reactive groups that react with each other to form X of the general formula (1).

As a specific example of the method for producing the organic phosphorus compound (1), the method for producing the organic phosphorus compound A1 will be described below.

(1) Intermediate (a)
After adding cupric bromide to a cyclohexene solution of 4-carboxy-2,2,6,6-tetramethylpiperidin 1-oxyl free radical, t-butyl hydroperoxide is slowly added. Then, a 20% aqueous sodium sulfite solution is added and stirred overnight, the aqueous phase is separated, the organic phase is washed with water and salt water, and then concentrated with a rotary evaporator. The residue is dissolved in methanol and the mixture to which butylamine and Pd-supported charcoal are added is hydrogenated to obtain 4-carboxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy as intermediate (a). ..

(2) Intermediate (b)
As the diphenylphosphorochloridate used as the intermediate (b), a commercially available product can be used.

(3) Reaction of Intermediate (a) and Intermediate (b) Diphenylphosphorochloridate and toluene (intermediate (b)) are stirred in a four-necked flask to completely dissolve them. Then, 4-carboxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy (intermediate (a)) and triethylamine are placed in two dropping funnels and dropped to react. The solution after the reaction is neutralized with an aqueous hydrochloric acid solution, the organic layer is taken out, washed with water, the toluene is flushed under reduced pressure, the low boiling point composition is removed by steam distillation, and after filtration through Celite, the desired organic phosphorus compound A1 is obtained. obtain.

The organic phosphorus compound (1) can be identified by mass spectrometry (MS), ¹ H-NMR, ¹³ C-NMR, infrared spectroscopy (IR), or the like.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing a thermoplastic resin and a flame retardant, wherein the thermoplastic resin contains a polyolefin resin as a main component, and the flame retardant is organic. It is characterized by containing a phosphorus compound (1).

In addition to the thermoplastic resin and the flame retardant, the thermoplastic resin composition of the present invention can optionally contain various additives generally contained in the thermoplastic resin composition. Hereinafter, each component in the thermoplastic resin composition of the present invention will be described.

(Thermoplastic resin)
The thermoplastic resin contained in the thermoplastic resin composition of the present invention contains a polyolefin resin as a main component. The content of the polyolefin-based resin in the thermoplastic resin is 50% by mass or more, preferably 60% by mass or more, and more preferably 80% by mass or more with respect to the total amount of the thermoplastic resin. The upper limit of the content of the polyolefin resin in the thermoplastic resin is 100% by mass. That is, the thermoplastic resin may consist only of the polyolefin-based resin.

The content of the thermoplastic resin in the thermoplastic resin composition of the present invention is the amount obtained by subtracting the content of the flame retardant and various other additives optionally contained from the thermoplastic resin composition.

<Polyolefin resin>
The polyolefin-based resin is a homopolymer or a copolymer polymerized with an olefin as a main component of a monomer component. In the present specification, "olefin" refers to an aliphatic chain unsaturated hydrocarbon having one double bond.

Here, the main component constituting the resin (polymer) means a component that is 50% by mass or more of all the monomer components constituting the polymer. The polyolefin-based resin is a homopolymer or copolymer containing olefin in all monomer components, preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass. be.

The olefin copolymer includes a copolymer of an olefin and another olefin, or a copolymer of an olefin and another monomer copolymerizable with the olefin. The content of the other monomer in the polyolefin resin is preferably 30% by mass or less, more preferably 0 to 20% by mass, based on all the monomer components.

As the olefin, an α-olefin having 2 to 12 carbon atoms is preferable. Examples of the olefin include ethylene, propylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, 1-decene and the like. When polymerizing the polyolefin resin, one type of olefin may be used alone, or two or more types may be used in combination.

Examples of other monomers copolymerizable with the olefin include cyclic olefins such as cyclopentene and norbornene, and diene such as 1,4-hexadiene and 5-ethylidene-2-norbornene. The other monomers may be used alone or in combination of two or more when polymerizing the polyolefin resin.

Preferable specific examples of the polyolefin-based resin are polyethylene resins containing ethylene as a main component, such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE); polypropylene (propylene alone). Polymer), ethylene-propylene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer, and propylene-based polypropylene resin such as ethylene-propylene-diene copolymer; polybutene; In addition, polypentene and the like can be mentioned.

As the polyolefin-based resin, a polyethylene-based resin and a polypropylene-based resin are preferable, and a polypropylene-based resin is more preferable. The stereoregularity of the structure derived from propylene in the polypropylene-based resin may be any of isotactic, syndiotactic, and atactic. As the polypropylene-based resin, polypropylene is more preferable.

The polyolefin-based resin contained in the thermoplastic resin may be one kind or two or more kinds.

<Other thermoplastic resins>
Examples of the thermoplastic resin other than the polyolefin resin that can be contained in the thermoplastic resin include polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), and polycarbonate resin.

(Flame retardants)
The flame retardant contained in the thermoplastic resin composition of the present invention contains an organic phosphorus compound (1). The flame retardant may consist of only the organic phosphorus compound (1), or may contain other flame retardant compounds other than the organic phosphorus compound (1) as long as the effects of the present invention are not impaired. Examples of other flame retardant compounds include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, condensed phosphoric acid esters, and intomescent flame retardants.

In the thermoplastic resin composition of the present invention, the content of the organic phosphorus compound (1) as a flame retardant is within the range of 10 to 40% by mass with respect to the total amount of the thermoplastic resin and the organic phosphoric acid compound (1). It is preferable to be in. When the content of the organic phosphoric acid compound (1) in the thermoplastic resin composition is within the above range, the occurrence of bleed-out of the organic phosphoric acid compound (1) is suppressed and the length is long in the obtained molded product. It is stable and easily develops flame retardancy even after a period of use.

When the flame retardant contains other flame retardant compounds, the content thereof is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of the flame retardant. It is particularly preferable that the flame retardant does not contain other flame retardant compounds.

(Other additives)
Examples of additives other than flame retardants that can be optionally contained in the thermoplastic resin composition of the present invention include antioxidants, fillers, crystal nucleating agents and the like. The content of other additives in the thermoplastic resin composition of the present invention is within a range that does not impair the effects of the present invention, for example, in the range of about 0 to 30% by mass with respect to the total amount of the thermoplastic resin composition. It is preferably in the range of 0 to 20% by mass. Moreover, it is preferable that the total is 30% by mass or less.

(Manufacturing of thermoplastic resin composition)
The thermoplastic resin composition of the present invention includes the above-mentioned thermoplastic resin containing a polyolefin resin as a main component and an organic phosphoric acid compound (1), and other flame-retardant compounds which may be contained as needed. It can be obtained by melt-kneading other components. The method of melt-kneading is not particularly limited, and a known melt-kneading method can be used.

To give a specific example, each component is premixed using various mixers such as a tumbler and a high-speed mixer known as a Henschel mixer, and then a Banbury mixer, a roll, a plastograph, a single-screw extruder, and a twin-screw extruder. , And a method of melt-kneading with a kneading device such as a kneader. Among these, a manufacturing method using a twin-screw extruder is more preferable, and a manufacturing method using a twin-screw extruder is further preferable because the production efficiency is high. Each component can be melt-kneaded using an extruder, the kneaded product can be extruded into a strand shape, and then the kneaded product extruded into a strand shape can be processed into pellets or flakes.

The temperature at the time of melt-kneading is, for example, 150 to 280 ° C., and is appropriately selected depending on the polyolefin-based resin used. When a polypropylene-based resin is used as the polyolefin-based resin, the temperature at the time of melt-kneading is preferably 180 ° C. to 270 ° C., more preferably 190 to 230 ° C.

The thermoplastic resin composition of the present invention can take various forms such as powder, granules, tablets, pellets, flakes, fibrous, and liquid.

The content of the organic phosphoric acid compound (1) in the thermoplastic resin composition can be measured as follows.

The thermoplastic resin composition is extracted with a Soxhlet extractor (solvent: THF) to extract the elution component in the thermoplastic resin composition. The elution component contains an organic phosphoric acid compound (1). After separation by preparative HPLC (High Performance Liquid Chromatography), the organic phosphoric acid compound is analyzed by thermal weight analysis, IR, NMR, etc. Identify the structure of (1). Phosphorus concentration is also measured by X-ray fluorescence analysis as described in E.P. Bertin's Principles and Practice of Xray Spectrometric Analysis Second Ed. (Plenum Press 1984). The obtained phosphorus concentration is converted into the structure of the identified organic phosphoric acid compound (1), and the content of the organic phosphoric acid compound (1) in the thermoplastic resin composition is calculated.

When the thermoplastic resin composition of the present invention is used, the main component is a polyolefin resin which has flame retardancy due to the action of the organic phosphoric acid compound (1) and whose flame retardancy is guaranteed for a long period of time. Molded products can be manufactured.

Here, flame retardancy is one of flame resistance, and refers to a property that burns slowly but continues to burn to some extent. Regarding the evaluation of flame resistance, there are JIS, ASTM, etc., but in general, UL standard is particularly emphasized. The UL standard is a standard established by "Underwriters Laboratorie" in the United States and evaluated by the company.

In a molded product molded from the thermoplastic resin composition of the present invention, when evaluated as a test piece of a predetermined size according to the above UL standard, it is preferably evaluated as passing by UL94HB, and passing by UL94V-2. It is more preferable that it is evaluated as passing, and it is further preferable that it is evaluated as passing by UL94V-0.

Further, when the thermoplastic resin composition of the present invention is used, the organic phosphoric acid compound (1), which is a flame retardant, can be bleeded out by the usual molding method described below while having the above-mentioned sufficient flame retardancy. A molded product that is suppressed and has a good appearance in which the occurrence of "burrs", "burns", etc. is suppressed and also has excellent mechanical strength such as bending strength can be obtained.

(Molding)
A molded product can be produced using the thermoplastic resin composition of the present invention. From this molded product, a product having flame retardancy can be obtained. When producing a molded product, the thermoplastic resin composition can be melted and molded in various molding machines. The molding method can be appropriately selected depending on the form and application of the molded product, and examples thereof include injection molding, extrusion molding, compression molding, blow molding, calendar molding, and inflation molding. Further, the sheet-shaped or film-shaped molded product obtained by extrusion molding, calendar molding or the like can be subjected to secondary molding such as vacuum forming or pressure molding.

The molded product molded from the thermoplastic resin composition of the present invention is not particularly limited, and for example, electrical / electronic parts, electrical components, exterior parts, interior parts, etc. in the fields of home appliances and automobiles, and various packagings. Materials, household appliances, office supplies, piping, agricultural materials, etc. can be mentioned.

[Electronics]
The present invention can provide an electronic device characterized in that the molded product is used as a part. Electronic devices are not particularly limited, but computers, scanners, copiers, printers, facsimile machines, OA devices such as MFPs (Multi Function Peripherals) that have these functions, and digital printing for commercial printing. The system etc. can be mentioned.

The molded product molded from the thermoplastic resin composition of the present invention is preferably used as an exterior part of an electronic device. The large copying machine shown in FIG. 1 will be described as an example. FIG. 1 is a schematic perspective view of the large copier 10. As shown in FIG. 1, the large copier 10 is exteriorized by exterior parts G1 to G9. A molded product molded from the thermoplastic resin composition of the present invention can be used for such an exterior component.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, the indication of "parts" or "%" is used, but unless otherwise specified, it indicates "parts by mass" or "% by mass".

[Production example of organophosphate compound (1)]
(Production of Organophosphate Compound A1)
The organic phosphoric acid compound A1 was produced as follows.

(1) Synthesis of cyclohexyloxy field 4-carboxy-2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Kasei Co., Ltd.) 98.2 g (0.49 mol), cyclohexene 370 g (4.52 mol) After adding 1.01 g (4.5 mmol) of cupric bromide to the solution, the temperature was increased to 60 ° C., and 49 g (0.38 mol) of t-butyl hydroperoxide was slowly added. The mixture was maintained at 60 ° C. for a total of 3 hours. Then, the mixture was cooled to 25 ° C., and 280 g of a 20% aqueous sodium sulfite solution was added. After stirring overnight, the aqueous phase was separated, the organic phase was washed with water and brine, and then concentrated on a rotary evaporator. The residue was dissolved in 1200 mL of methanol and 35.8 g (0.49 mol) of butylamine and 16.3 g of Pd-supported charcoal (10%) were added. The mixture was stirred at 25 ° C. for 1.5 hours and then hydrogenated at 50 ° C./10 bar (hydrogen pressure) for 1.5 hours. The mixture is filtered and the filtrate is concentrated. The residue was distilled to obtain 89.9 g (65%) of 4-carboxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy.

(2) Synthesis of organophosphate compound A1 Diphenylphosphorochloride (DPC, manufactured by Daihachi Chemical Industry Co., Ltd.) 42.2 g (0.2, mol) and 30 g of toluene were stirred in a four-necked flask to complete the process. It was dissolved. Then, 56.5 g (0.2 mol) of 4-carboxy-2,2,6,6-tetramethylpiperidine 1-cyclohexyloxy compound obtained in (1) above and 21.2 g of triethylamine were placed in two dropping funnels. (0.21 mol) was added thereto, and the mixture was added dropwise at 5 to 10 ° C. over 3 hours under cooling with a cryogen. After the dropping, the mixture was allowed to stand at room temperature, reacted for 3 hours, and then stirred at 40 ° C. for 2 hours. After neutralizing the solution after the reaction with an aqueous hydrochloric acid solution, the organic layer is taken out, washed with water, the toluene is flushed under reduced pressure, the low boiling point composition is removed by steam distillation, and after filtration through Celite, 80.9 g of the target compound is added. (94%) obtained.

The obtained compound was ^{measured by IR, 1} H-NMR, and ¹³ C-NMR, and was identified as an organic phosphoric acid compound A1 from the results.

(Production of Organophosphate Compound A2)
The organic phosphoric acid compound A2 was produced as follows.

(1) Synthesis of cyclohexyloxy compound 4-Hydroxy-2,2,6,6-tetramethylpiperidine1-oxylfree instead of 4-hydroxy-2,2,6,6-tetramethylpiperidine1-oxylfree radical 4-Hydroxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy compound in the same manner as the cyclohexyloxy intermediate of A1 except that 84.4 g (0.49 mol) of radical (manufactured by Tokyo Kasei Co., Ltd.) was used. Was obtained in an amount of 87.3 g (70%).

(2) Synthesis of organophosphate compound A2 Diphenylphosphorochloride (DPC, manufactured by Daihachi Chemical Industry Co., Ltd.) 53.7 g (0.2, mol) and 40 g of toluene were stirred in a four-necked flask to complete the process. It was dissolved. After that, 50.9 g (0.2 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-cyclohexyloxy compound obtained in (1) above and 21.2 g of triethylamine (21.2 mol) were placed in two dropping funnels. 0.21 mol) was added, and the mixture was added dropwise over 2 hours while keeping the temperature below 10 ° C. under cooling with a freezing bath. After the dropping, the mixture was allowed to stand at room temperature, reacted for 2 hours, and then stirred at 50 ° C. for 2 hours. The solution after the reaction is neutralized with an aqueous hydrochloric acid solution, the organic layer is taken out, washed with water, the toluene is flushed under reduced pressure, the low boiling point composition is removed by steam distillation, and after filtration through Celite, 87.8 g of the target compound is added. (90%) obtained.

The obtained compound was ^{measured by IR, 1} H-NMR, and ¹³ C-NMR, and was identified as an organic phosphoric acid compound A2 from the results.

(Production of Organophosphate Compound A3)
The organic phosphoric acid compound A3 was produced as follows.

(1) Synthesis of cyclohexyloxy compound 63.6 g (0.25 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy compound, which is a synthetic intermediate of the organic phosphoric acid compound A2, triethylamine 28 .3 g (0.28 mol) and 40 g of toluene were placed in a 4-neck flask and cooled to 10 ° C. or lower with stirring. 32.1 g (0.25 mol) of 4-chlorophenol was added to the dropping funnel, and the mixture was added dropwise over 3 hours while maintaining the liquid temperature at 10 ° C. or lower. The reaction was terminated by stirring at room temperature for 3 hours and at 50 ° C. for 2 hours. After neutralizing the reaction solution with an aqueous hydrochloric acid solution, the organic layer is taken out, washed with water, the toluene is flushed under reduced pressure, the low boiling point composition is removed by steam distillation, and after filtration through Celite, the target 4-hydroxyphenyloxy-2 is used. , 2,6,6-Tetramethylpiperidin 1-cyclohexyloxy compound was obtained in an amount of 84 g (97%).

(2) Synthesis of organophosphate compound A3 Diphenylphosphorochloride (DPC, manufactured by Daihachi Chemical Industry Co., Ltd.) 53.7 g (0.2, mol) and 30 g of toluene were stirred in a four-necked flask to complete the process. It was dissolved. Then, in two dropping funnels, 69.3 g (0.2 mol) of 4-hydroxyphenyloxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy compound obtained in (1) above, and triethylamine 21. 2 g (0.21 mol) was added thereto, and the mixture was added dropwise at 5 to 10 ° C. over 3 hours under cooling with a cryogen. After the dropping, the mixture was allowed to stand at room temperature, reacted for 3 hours, and then stirred at 40 ° C. for 2 hours. After neutralizing the solution after the reaction with an aqueous hydrochloric acid solution, the organic layer is taken out, washed with water, the toluene is flushed under reduced pressure, the low boiling point composition is removed by steam distillation, and after filtration through Celite, 110.1 g of the target compound is added. (93%) obtained.

The obtained compound was ^{measured by IR, 1} H-NMR, and ¹³ C-NMR, and was identified as an organic phosphoric acid compound A3 from the results.

(Production of Organophosphate Compound A4)
The organic phosphoric acid compound A4 was produced as follows.

(1) Synthesis of cyclohexyloxy compound 4-Hydroxy-2,2,6,6-tetramethylpiperidine1-cyclohexyloxy compound was synthesized in the same manner as in the synthesis of cyclohexyloxy compound in the organic phosphoric acid compound A2.

(2) Synthesis of phosphochloridate In a four-necked flask equipped with a stirrer, a thermometer, a dropping device, a hydrochloric acid recovery device and a reflux tube, 42.2 g (0.25 mol) of phosphorus oxychloride (manufactured by Kanto Chemical Co., Ltd.), The mixture was filled with 24.0 g (0.5 mol) xylene of propanol and 0.35 g of anhydrous magnesium chloride, and the mixed solution was heated to 160 ° C. over 3 hours with stirring under a nitrogen atmosphere, and then heated to 160 ° C. for 1 hour. The reaction was carried out at a temperature (160 ° C.). The pressure was reduced at the same temperature (160 ° C.) to remove by-product hydrogen chloride gas and xylene to obtain 52.5 g (97%) of dipropylphosphochloride.

(3) Synthesis of organic phosphate compound A4 Except that 53.7 g of diphenylphosphochloridate (DPC, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed to 43.3 g of dipropylphosphorochloridate synthesized as described in (2) above. In the same manner as in the synthesis of the organic phosphate compound A2, the 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-cyclohexyloxy compound obtained in (1) above and dipropylphosphorochloridate were used. The reaction gave 78.0 g (93%) of the compound.

The obtained compound was ^{measured by IR, 1} H-NMR, and ¹³ C-NMR, and was identified as an organic phosphoric acid compound A4 from the results.

(Production of Organophosphate Compound A5)
The organic phosphoric acid compound A5 was produced as follows.

(1) Synthesis of propyloxy field In a 300 mL stainless steel autoclave, 6 g (0.03 mol) of 4-carboxy-2,2,6,6-tetramethylpiperidin 1-oxyl free radical, CuBr ₂ 198 mg (0.9 mmol). ) And Bu ₄ NBr 286 mg (0.9 mmol) were added. The autoclave was sealed and 38.6 g (920 mmol) of propylene was added. The reaction was heated to 70 ° C. (pressure about 28 bar). After reaching the temperature, 7.6 g (58.8 mmol) (70% aqueous solution) of t-BuOOH was added for 2.5 hours, and the mixture was further stirred for 2 hours. After that, the pressure in the autoclave was released. The reaction mixture was rinsed with 50 mL of dichloromethane and removed. The solvent was removed from the reaction mixture and the crude product (7.1 g) was purified by flash chromatography (silica gel, hexane / ethyl acetate = 3/1) and 4-carboxy-1propyloxy-2,2,6. 4.5 g (62%) of 6-tetramethylpiperidin was obtained.

(2) Synthesis of phosphorochloridate 42.2 g (0.2 mol) of monophenylphosphologi chloride in a four-necked flask equipped with a stirrer, a thermometer, a dropping device, a hydrochloric acid recovery device and a reflux tube (MPC, (Manufactured by Daihachi Chemical Industry Co., Ltd.), p-cresol 21.6 g (0.2 mol) xylene 2 g and anhydrous magnesium chloride 0.28 g are filled, and the mixed solution is stirred under a nitrogen atmosphere to 160 ° C. over 3 hours. The temperature was raised and heated, and then the reaction was carried out at the same temperature (160 ° C.) for 1 hour. The pressure was reduced at the same temperature (160 ° C.) to remove by-product hydrogen chloride gas and xylene to obtain 53.7 g of (phenylp-methylphenyl) phosphorochloridate.

(3) Synthesis of Organophosphorus Compound A5 50 g (0.18 mol) of (phenyl p-methylphenyl) phosphorochloridate obtained in (2) above and 30 g of toluene were stirred in a four-necked flask to complete the process. Was dissolved in. After that, 43.0 g (0.18 mol) of 4-carboxy-1propyloxy-2,2,6,6-tetramethylpiperidine obtained in (1) above and 20.2 g of triethylamine (0. 20 mol) was added thereto, and the mixture was added dropwise at 5 to 10 ° C. over 3 hours under cooling with a cryogen. After the dropping, the mixture was allowed to stand at room temperature, reacted for 3 hours, and then stirred at 40 ° C. for 2 hours. After neutralizing the solution after the reaction with an aqueous hydrochloric acid solution, the organic layer is taken out, washed with water, the toluene is flushed under reduced pressure, the low boiling point composition is removed by steam distillation, and after filtration through Celite, 80.2 g of the target compound is added. (91%) obtained.

The obtained compound was ^{measured by IR, 1} H-NMR, and ¹³ C-NMR, and was identified as an organic phosphoric acid compound A5 from the results.

[Preparation of thermoplastic resin composition]
(Thermoplastic resin)
The following commercially available products were prepared as thermoplastic resins.
1. 1. Polyolefin resin High density polyethylene (PE): HI-ZEX (HDPE) 1300J (Product name, manufactured by Prime Polymer Co., Ltd.)
Polypropylene resin (PP): Prime Polypro J715M (product name, manufactured by Prime Polymer Co., Ltd.)

2. Other thermoplastic resins ABS resin: Santac AT-05 (product name, manufactured by Nippon A & Al Co., Ltd.)
Polycarbonate resin (PC): Toughlon A-1900 (product name, manufactured by Idemitsu Kosan Co., Ltd.)

(Flame retardants and hindered amines)
As the flame retardant, the organic phosphoric acid compounds A1 to A5, which are the organic phosphoric acid compounds (1) of the present invention obtained above, and the commercially available organic phosphoric acid compounds for comparative examples shown below were used. In addition, the commercially available hindered amines shown below were used as other additives.

<Organophosphate compounds for comparative examples>
As the organic phosphoric acid compound for the comparative example, three kinds of commercially available organic phosphoric acid esters having the following structures were prepared. TPP is a triphenyl phosphate manufactured by Daihachi Kagaku Co., Ltd. PX-200 (product name) is an aromatic condensed phosphoric acid ester manufactured by Daihachi Chemical Industry Co., Ltd. FP-500 (Adecaster FP-600, product name, viscosity (25 ° C.) 18,000 to 20,000 mPa · s) is an aromatic condensed phosphate ester manufactured by Adeca. In addition, n in the formula is a number in which the viscosity (25 ° C.) is in the above range.

<Hindered Amin>
As a hindered amine, a commercially available FlamestabNOR116FF (product name, manufactured by BASF) having the structure shown below was prepared.

(Preparation of thermoplastic resin composition)
As a pre-drying before kneading, the thermoplastic resin, flame retardant and other additives were dried at 80 ° C. for 4 hours. Then, it was weighed by the component ratio (part by mass) shown in Table I and dry-blended.

Next, the mixture obtained by dry blending was supplied at 10 kg / h from the raw material supply port (hopper) of the twin-screw extrusion kneader (KTX-30; Kobe Steel, Ltd.), and the temperature of the cylinder was set to 190 ° C. and the screw. The melt kneading was carried out under the condition that the rotation speed of the above was 200 rpm. The molten resin after kneading was cooled in a water tank at 30 ° C. and then pelletized with a pelletizer to obtain thermoplastic resin compositions 1 to 17. The thermoplastic resin compositions 1 to 10, 13 and 14 correspond to the thermoplastic resin compositions of the present invention, the thermoplastic resin compositions 11 and 12 are reference examples, and the thermoplastic resin compositions 15 to 17 are comparative. This is an example.

<Confirmation of composition of thermoplastic resin composition>
The constituent components and the mass ratio in the thermoplastic resin composition can be confirmed by the following method. In this method, the mass ratio can be confirmed as the same value as the charged amount.
(1) Identification of constituent components in the thermoplastic resin composition The thermoplastic resin composition is extracted with a Soxley extractor (solvent: THF) for 5 hours to extract the elution components in the thermoplastic resin composition. .. The extract is separated by preparative HPLC and then identified using ^{IR, 1} H-NMR, and ^{13 C-NMR.}

(2) Mass ratio of each component The organic phosphoric acid compound in the thermoplastic resin composition is the molecular weight of the identified compound by measuring the phosphorus element content using an ICP emission spectrometer (SPS4000, manufactured by Seiko Electronics Co., Ltd.). More demanded. The phosphorus content was determined by the calibration curve method using a reagent for atomic absorption spectrometry (manufactured by Kanto Chemical Co., Inc.) as the standard solution.

<Evaluation>
The thermoplastic resin compositions 1 to 17 obtained above were evaluated by performing the following evaluations 1 to 5. The results are shown in Table I together with the composition of the thermoplastic resin composition and the cylinder set temperature at the time of molding.

(Evaluation 1: Surface stickiness)
Each of the obtained pelletized thermoplastic resin compositions 1 to 17 was dried at 80 ° C. for 4 hours, and then using an injection molding machine (J55ELII, manufactured by Japan Steel Works, Ltd.), the cylinders shown in Table I. Molding was performed with the set temperature and the mold temperature set to 50 ° C. to obtain test pieces having a size of 80 mm in length, 10 mm in width, and 4.0 mm in height.

The above test piece was heat-treated at 80 ° C. and 90% RH for 48 hours using a constant temperature and humidity chamber, and then the surface was visually observed. The following judgments were made regarding the exudation (stickiness) of the flame retardant or the flame retardant and the additive. Those above 〇 were accepted.

◎: No flame retardant exudation (stickiness) 〇: Flame retardant exudation occurred slightly, but there was no stickiness and there was no problem in use △: Flame retardant exudation occurred after heat treatment , Sticky ×: The flame retardant has already exuded before the heat treatment, and it is sticky.

(Evaluation 2: Initial flame retardancy)
Each of the obtained pelletized thermoplastic resin compositions 1 to 17 was dried at 80 ° C. for 4 hours, and then using an injection molding machine (J55ELII, manufactured by Japan Steel Works, Ltd.), the cylinders shown in Table I. Molding was performed at a set temperature and a mold temperature of 50 ° C. to obtain a strip-shaped test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.6 mm.

Next, the obtained test piece was subjected to humidity control for 48 hours in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and the UL94 test (plastic material for equipment parts) defined by the US Underwriters Laboratories (UL). The flame retardancy test was conducted in accordance with the combustion test). For the test, the UL94V test method was first carried out, and the UL94HB test was carried out on the material which did not reach V-2 at UL94V, and the order of flame retardancy was confirmed. Then, the flame retardancy was evaluated based on the following evaluation criteria. Δ That is, if the flame retardancy is HB or higher, the result is acceptable.

⊚: V-0 (pass)
◯: V-1 or V-2 (passed)
Δ: HB (passed)
×: Non-standard (HB test also failed)

(Evaluation 3: Flame retardancy after light resistance test)
A test piece prepared by the same method as in Evaluation 2 above was exposed to a Ci4000 weatherometer (manufactured by Atlas) for 30 days (1 W / m ^{2 at} 420 nm, tank temperature 25 ° C., humidity 50%). RH). Then, the same flame retardancy test as in Evaluation 3 was carried out, and the flame retardancy was evaluated after the light resistance test.

(Evaluation 4: Bending strength)
A test piece similar to the test piece used for the evaluation of surface stickiness in the above evaluation 1 was molded using a mold. As for the number of moldings, 300 shots were discarded and then 100 shots were continuously molded. The variation XTS (%) of the bending strength of the obtained 100 molded products was calculated from the following formula and evaluated according to the following evaluation criteria. ○ If it is above, it is judged that there is no problem in practical use.

XTS (%) = (TRmax-TRmin) / (TRav) x 100
In the above formula, TRmax represents the maximum value (MPa) of the bending strength of 100 molded bodies, TRmin represents the minimum value (MPa) of the bending strength of 100 molded bodies, and TRav is 100. It represents the average value (MPa) of the bending strength of each molded body. Here, the bending strength of the molded product is a value measured based on JIS K7171.

⊚: TRav is 20 MPa or more and XTS is less than 0.5% ◯: TRav is 20 MPa or more and XTS is 0.5% or more and less than 5% Δ: TRav is 20 MPa or more and XTS is 5% or more and less than 15% × : TRav is less than 20MPa, or XTS is 15% or more

(Evaluation 5: Evaluation of production of exterior parts)
Each of the obtained pellet-shaped thermoplastic resin compositions 1 to 17 was dried at 80 ° C. for 5 hours with a hot air circulation type dryer. After drying, using an injection molding machine (J1300E-C5 manufactured by Japan Steel Works, Ltd.), a simulated molded product assuming the exterior part G8 of the large copier shown in FIG. 1 is shown in Table I for the cylinder temperature and mold temperature. It was molded at 80 ° C., and a sample was taken from the central part. The appearance of the obtained sample was visually observed and evaluated according to the following criteria. In this test, surface stickiness was not included in the evaluation. ○ If it is above, it is judged that there is no problem in practical use.

◎: No appearance defect 〇: Slightly “burnt” or “burr” is recognized, but there is no problem as a product ×: “burnt” or “burr” is recognized and cannot be used as a product

From Table I, the organophosphorus compound of the present invention has high compatibility with the polyolefin resin, and exhibits stable flame retardancy for a long period of time in a molded product of a thermoplastic resin composition containing the polyolefin resin together with the polyolefin resin. You can see that.

10: Large copier G1 to G9: Exterior parts

Claims (6)

An organic phosphorus compound having a structure represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group or an alkoxy group which may have a substituent. R ² and R ³ each independently have a substituent. May represent an alkyl group, an aryl group or an alkoxy group. R ² and R ³ may be the same or different. X represents a divalent linking group.) The organic phosphorus compound according to claim 1, which has a structure represented by the following general formula (2).

(In the general formula (2), R ⁴ is an aryl group which may have a substituent. X represents a divalent linking group.) A thermoplastic resin composition containing a thermoplastic resin and a flame retardant.
The thermoplastic resin contains a polyolefin resin as a main component and contains
A thermoplastic resin composition, wherein the flame retardant contains the organic phosphorus compound according to claim 1 or 2. The thermoplastic resin according to claim 3, wherein the content of the organic phosphoric acid compound is in the range of 10 to 40% by mass with respect to the total amount of the thermoplastic resin and the organic phosphoric acid compound. Composition. The thermoplastic resin composition according to claim 3 or 4, wherein the polyolefin-based resin is a polypropylene-based resin. An electronic device characterized in that the molded product of the thermoplastic resin composition according to any one of claims 3 to 5 is used as a part.

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