JP2018150418A - Flame-retardant master batch, flame-retardant resin composition, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant master batch which prevents occurrence of a discomfort odor in melt-kneading, is excellent in work environmental properties, has good workability, and can impart excellent flame retardancy to a thermoplastic resin.SOLUTION: A flame-retardant master batch contains a polyolefin resin, a first flame retardant represented by formula (1), a second flame retardant represented by formulae (2) and (3), and a compatibilizing agent made from a hindered amine compound.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant masterbatch, a flame retardant resin composition, and a molded article.

  Polyolefin resins such as polyethylene resins and polypropylene resins are widely used in various fields such as home appliances, automobiles, household goods, and office supplies. Since the polyolefin resin has a property of being easily combusted, it is required to be flame retardant in various applications from the viewpoint of safety.

  Conventionally, polyolefin resins include bromine compound flame retardants such as polybromobiphenyl (PBB) and polybromodiphenyl ether (PBDE), or a combination of these bromine compound flame retardants and antimony compounds such as antimony trioxide. It has been used from the viewpoint of flame retardancy efficiency and cost. However, in recent years, the use of halogen-containing compounds such as bromine-based flame retardants and antimony-based compounds has been pointed out with respect to environmental and health problems. For this reason, the alternative flame retardant which can provide a flame retardance effectively is calculated | required.

  There are various types of flame retardants, and until now, blending of various flame retardants with polyolefin resins has been studied. For example, for the purpose of providing a flame retardant resin composition having excellent environmental compatibility in addition to flame retardancy, a predetermined amount of each of synthetic resins such as polyethylene resins, layered silicates, and hindered amine compounds was blended. A flame retardant resin composition has been proposed (Patent Document 1). In addition, a resin composition containing a condensed phosphonate as a flame retardant has been proposed (Patent Document 2).

JP 2003-26938 A JP 2013-28731 A

  As a flame retardant expected to have high flame retardant performance, the present inventors have incorporated a hindered amine compound disclosed in paragraph [0053] of the specification of Patent Document 1 into a polypropylene resin as a flame retardant master batch. Was examined. As a result, it has been found that an unpleasant odor is generated during melt-kneading and molding. It is considered that the cause of the unpleasant odor is that the hindered amine compound was thermally decomposed.

  Incidentally, hindered amine compounds are widely used as light stabilizers (hindered amine light stabilizers; HALS). The amount used when a hindered amine compound is used as a light stabilizer is usually smaller than the amount used when used as a flame retardant. For this reason, in the molded article which consists of a resin composition which uses a hindered amine type compound as a light stabilizer, it is thought that the odor resulting from a hindered amine type compound hardly becomes a problem. However, when a hindered amine compound is used as a flame retardant, there is a concern about the generation of an unpleasant odor due to an increase in the amount used. In particular, since the flame retardant masterbatch usually contains a flame retardant at a higher concentration than the product, an unpleasant odor is more likely to occur.

  If an unpleasant odor occurs during the melt-kneading of the components of the flame-retardant resin composition or the molding process of the flame-retardant resin composition, the product (molded product) molded from the flame-retardant resin composition also has an odor. May remain. For this reason, it becomes difficult to employ | adopt such a flame-retardant resin composition and its molded article for the use used in sealed spaces, such as indoor or a vehicle interior material.

  On the other hand, the masterbatch or resin composition containing the condensed phosphonate ester proposed in Patent Document 2 as a flame retardant is uncomfortable as when the hindered amine compound disclosed in Patent Document 1 is used as a flame retardant. Odor is unlikely to occur. However, as a result of studies by the present inventors, it has been found that the condensed phosphonic acid ester cannot be said to have good compatibility with the polyolefin resin. That is, it has been found that if a sufficient amount of the condensed phosphonic acid ester exhibiting flame retardancy is added to the polyolefin resin, problems such as deterioration of workability such as a bleed phenomenon easily occur.

  The present invention has been made in view of such problems of the prior art, and the problem is that an unpleasant odor is less likely to occur during production such as melt-kneading, and is excellent in work environment. Another object of the present invention is to provide a flame retardant masterbatch having good processability and capable of imparting excellent flame retardancy to a thermoplastic resin. Furthermore, the place made into the subject of this invention is providing the flame-retardant resin composition obtained using said flame-retardant masterbatch, and its molded article.

That is, according to the present invention, the following flame retardant master batch is provided.
[1] containing a polyolefin-based resin, a first flame retardant represented by the following formula (1), a second flame retardant represented by the following formulas (2) and (3), and a compatibilizer, The compatibilizer is at least one of a hindered amine compound represented by the following general formula (4) and a hindered amine compound represented by the following general formula (5), and the content of the first flame retardant is: A flame retardant masterbatch having a content of 7 to 18% by mass and a content of the second flame retardant of 5% by mass or less.

（前記式（２）中のＲは、前記式（３）で表される基であり、前記式（３）中の（＊）は、前記式（２）中のＲが結合しているＮとの結合を表す）

(R in the formula (2) is a group represented by the formula (3), and (*) in the formula (3) is N to which R in the formula (2) is bonded. Represents a bond with

（前記一般式（４）中、Ｒ₁は、ポリオレフィンワックスに由来するアルキル基を表し、Ｒ₂は、置換されていてもよい炭素原子数１〜２０のアルキル基を表す）

(In the general formula (4), R ₁ represents an alkyl group derived from a polyolefin wax, and R ₂ represents an optionally substituted alkyl group having 1 to 20 carbon atoms)

（前記一般式（５）中、Ｒ₃は、置換されていてもよい炭素原子数１〜２０のアルキル基を表し、ｎは２〜４の整数を表し、Ｒ₄は、括弧内のｎ個の基が結合する、置換されていてもよい２〜４価のアシル基を表す）

(In the general formula (5), R ₃ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, n represents an integer of 2 to 4, and R ₄ represents n in parentheses. Represents an optionally substituted divalent to tetravalent acyl group to which

[2] The flame-retardant masterbatch according to [1], wherein the content of the compatibilizer is 1 to 10% by mass.
[3] The above-mentioned [1] or [2], wherein the compatibilizer is at least one of a compound represented by the following formula (4-1) and a compound represented by the following formula (5-1). Flame retardant masterbatch.

Moreover, according to this invention, the flame retardant resin composition shown below and a molded article using the same are provided.
[4] A flame-retardant resin composition comprising a thermoplastic resin and the flame-retardant masterbatch according to any one of [1] to [3].
[5] A molded product comprising the flame retardant resin composition according to [4].
[6] The molded product according to [5], which is a film, a sheet, or a fiber.

  According to the present invention, an unpleasant odor is hardly generated at the time of production such as melt kneading, the work environment is excellent, the workability is good, and the thermoplastic resin has excellent flame retardancy. It is possible to provide a flame retardant masterbatch that is possible. Furthermore, according to this invention, the flame-retardant resin composition obtained using this flame-retardant masterbatch and its molded article can be provided.

  Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

<Flame-retardant masterbatch>
The flame-retardant masterbatch of this invention contains the 1st flame retardant represented by Formula (1), the 2nd flame retardant represented by Formula (2) and (3), and a compatibilizing agent. Hereinafter, details, such as a component which comprises the flame-retardant masterbatch of this invention, are demonstrated.

(First flame retardant)
The first flame retardant used in the flame retardant masterbatch of the present invention is a so-called phosphorus flame retardant represented by the following formula (1). The first flame retardant is less likely to generate an unpleasant odor during production such as melt kneading as compared to the hindered amine compound disclosed in Patent Document 1 and the like. For this reason, work environment property can be improved by mix | blending a 1st flame retardant. Furthermore, since it is difficult for odor to remain in the product (molded product), using the flame retardant masterbatch of the present invention, it is possible to produce a molded product that can be suitably used in an enclosed space such as indoors or vehicle interior materials. it can.

  As the first flame retardant represented by the formula (1), a synthetic product or a commercial product can be used. As a commercial item of the 1st flame retardant represented by Formula (1), brand name "Nonen 73" (made by Maruhishi Oil Chemical Co., Ltd.) etc. can be mentioned, for example.

  Content of the 1st flame retardant in a flame-retardant masterbatch is 7-18 mass%, Preferably it is 8-16 mass%. When the content of the first flame retardant is less than 7% by mass, it becomes difficult to produce a resin composition or a molded product having sufficient flame retardancy. On the other hand, if the content of the first flame retardant is more than 18% by mass, a bleed phenomenon or the like is likely to occur during kneading and workability is deteriorated.

(Second flame retardant)
The second flame retardant used in the flame retardant masterbatch of the present invention is a so-called nitrogen-based flame retardant represented by the following formulas (2) and (3). By blending a predetermined amount of the second flame retardant, a flame retardant masterbatch capable of producing a resin composition or molded article having excellent flame retardancy can be obtained.

  As the second flame retardant represented by the formulas (2) and (3), a synthetic product or a commercial product can be used. As a commercial item of the 2nd flame retardant represented by Formula (2) and (3), brand name "Flamestab NOR116" (made by BASF Corporation) etc. can be mentioned, for example.

  Content of the 2nd flame retardant in a flame-retardant masterbatch is 5 mass% or less, Preferably it is 3 mass% or less. If the content of the second flame retardant is more than 5% by mass, an unpleasant odor is likely to occur during melt-kneading and the like, and the work environment is reduced. In addition, there is a possibility that unpleasant odors may remain in the resin composition or molded product obtained by using a flame retardant masterbatch containing an excessive amount of the second flame retardant. It becomes difficult to do. In addition, although it does not specifically limit about the minimum of content of the 2nd flame retardant in a flame-retardant masterbatch, By making it 1.5 mass% or more, the more superior flame retardance is provided to a thermoplastic resin. This is preferable because it can be performed.

(Compatibilizer)
The flame retardant masterbatch of the present invention contains at least one compatibilizer of a hindered amine compound represented by the following general formula (4) and a hindered amine compound represented by the following general formula (5). By including these compatibilizers, problems such as bleeding phenomenon occur during melt-kneading even when a sufficient amount of condensed phosphonic acid ester that exhibits flame retardancy is blended with the polyolefin resin. It becomes difficult and workability can be improved.

In General Formula (4), R ₁ represents an alkyl group derived from a polyolefin wax, and R ₂ represents an optionally substituted alkyl group having 1 to 20 carbon atoms. The number of carbon atoms of the optionally substituted alkyl group represented by R ₂ is preferably 5 to 20, more preferably 10 to 20, and particularly preferably 15 to 18.

In the general formula (5), R ₃ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, n represents an integer of 2 to 4, and R ₄ represents n groups in parentheses. Represents a divalent to tetravalent acyl group which may be substituted. The number of carbon atoms of the optionally substituted alkyl group represented by R ₃ is preferably 5 to 20, more preferably 7 to 18, and particularly preferably 8 to 15. n is preferably 2, and the divalent acyl group in that case preferably has 20 or less carbon atoms.

  Examples of the divalent acyl group include a carbonyl group, an oxalyl group, a malonyl group, a succinyl group, a glutaryl group, an adipoyl group, an octanedioyl group, a decandioyl group, a dodecandioyl group, a tetradecandioyl group, and a hexadecandioyl group. Saturated aliphatic acyl groups such as oil groups and octadecandioyl groups; unsaturated aliphatic acyl groups such as maleoyl groups, fumaroyl groups, citraconoyl groups, and mesaconoyl groups; aromatics such as phthaloyl groups, isophthaloyl groups, and terephthaloyl groups An acyl group etc. can be mentioned.

Next, the suitable example of the alkyl group derived from the polyolefin wax represented by R < ₁ > in General formula (4) is demonstrated. The number of carbon atoms of the alkyl group derived from the polyolefin wax represented by R ₁ is preferably 100 to 500, more preferably 100 to 300, and particularly preferably 150 to 250. When the number of carbon atoms of the alkyl group derived from the polyolefin wax represented by R ₁ is 100 to 500, the compatibility with the polyolefin resin is improved, and the flame retardant is easy to melt and knead and is easy to mold. Sex masterbatch.

  The alkyl group derived from the polyolefin wax may be linear or have a branched structure. The alkyl group derived from the polyolefin wax may be polar or nonpolar. The polar alkyl group is an alkyl group derived from a polar polyolefin wax. Examples of the polar polyolefin wax include those having a polar group grafted to the main chain of the polyolefin. Examples of the polar group include polar groups derived from α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and derivatives thereof. The alkyl group derived from the polyolefin wax preferably has a branched structure and is preferably nonpolar.

  Nonpolar polyolefin waxes can be produced, for example, by polymerization of olefin monomers such as ethylene, or by thermal decomposition of branched or unbranched polyolefins. Examples of non-polar polyolefin waxes include ethylene and propylene homopolymer and copolymer waxes. The nonpolar polyolefin wax is preferably a homopolymer of ethylene or propylene, or a copolymer of ethylene and propylene, more preferably a polyethylene wax, and still more preferably a polyethylene wax having a branched structure (branched polyethylene wax). is there. The polar polyolefin wax can be produced, for example, by copolymerization of an olefin monomer such as ethylene and a polar monomer such as the aforementioned α, β-unsaturated carboxylic acid or a derivative thereof.

  The average molecular weight of the hindered amine compound represented by the general formula (4) is preferably 2,000 to 7,000, and preferably 2,000 to 4,000 in order to improve compatibility with the polyolefin resin. More preferably, it is particularly preferably 2,500 to 3,500. The average molecular weight can be measured by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMS). Moreover, the decomposition start temperature of the hindered amine compound represented by the general formula (4) is preferably 240 ° C. or higher, and more preferably 250 ° C. or higher. The decomposition start temperature can be measured by differential scanning calorimetry (DSC).

The hindered amine compound represented by the general formula (4) is represented by, for example, the following general formula (4a) and at least one compound (N-oxylamine compound) represented by the following general formula (4b). It can be obtained by reacting with at least one compound (polyolefin wax). In general formula (4a) R ₁ R ₂ and in Formula (4b) in is the general formula (4) same meanings as R ₂ and R ₁ in.

  The N-oxylamine compound represented by the general formula (4a) and the polyolefin wax represented by the general formula (4b) can be reacted in the presence of a hydroperoxide and a metal compound as a catalyst, for example. . Examples of the hydroperoxide include hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and the like. Examples of the metal compound serving as a catalyst include molybdenum trioxide, vanadyl acetylacetonate, cobalt carbonyl and the like.

  Also, the N-oxylamine compound and the polyolefin wax can be reacted by a method of adding an N-oxylamine compound to the polyolefin wax and irradiating the resulting mixture with radiation. Further, the N-oxylamine compound and the polyolefin wax can be reacted also by a method of adding and mixing the N-oxylamine compound after irradiating the polyolefin wax. Examples of radiation include γ rays and electron beams.

As the hindered amine compound represented by the general formula (4) and the hindered amine compound represented by the general formula (5), both synthetic products and commercially available products can be used. As a commercial item of the hindered amine type compound represented by General formula (4), a brand name "Hostavin Now" (made by Clariant Chemicals) etc. can be mentioned, for example.
Moreover, as a commercial item of the hindered amine type compound represented by General formula (5), brand name "Adeka stab LA-81" (made by ADEKA) etc. can be mentioned.

  What is necessary is just to set suitably content of the compatibilizing agent in a flame-retardant masterbatch according to the quantity of the 1st flame retardant to mix | blend, and it is not specifically limited. Specifically, the content of the compatibilizer in the flame retardant masterbatch is preferably 1 to 10% by mass, and more preferably 1.5 to 8% by mass. If the content of the compatibilizing agent is less than 1% by mass, a bleed phenomenon or the like may occur somewhat easily during kneading. On the other hand, if the content of the compatibilizer is more than 10% by mass, the physical properties (for example, flame retardancy) of the obtained resin composition or molded product may be easily changed. In addition, formability such as spinnability may be easily lowered, and it may be disadvantageous in terms of cost.

(Polyolefin resin)
The flame retardant masterbatch of the present invention contains a polyolefin resin. The polyolefin resin is a homopolymer or copolymer polymerized with an olefin monomer as a main component of the monomer component. Here, the main component constituting the resin (polymer) refers to a component that is 50% by mass or more in all monomer components constituting the polymer. The polyolefin-based resin is a homopolymer or copolymer containing an olefin-based monomer in all monomer components, preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass. It is a coalescence.

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

  Examples of the olefin monomer include olefins such as ethylene and propylene, and 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, and 1-decene-1. And the like (for example, α-olefins having 2 to 12 carbon atoms). When the polyolefin resin is polymerized, one olefin monomer may be used alone, or two or more olefin monomers may be used.

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

  Specific examples of suitable polyolefin resins include polyethylene resins mainly composed of ethylene such as high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE); polypropylene (propylene) Homopolymer), ethylene-propylene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer, polypropylene-based resin mainly composed of propylene such as ethylene-propylene-diene copolymer; polybutene As well as polypentene. The flame retardant resin composition may contain one or more polyolefin resins.

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

(Other ingredients)
The flame retardant masterbatch can contain other components as necessary as long as the object of the present invention is not impaired. Examples of other components include a flame retardant aid, a filler for improving various properties such as mechanical properties, and other additives.

  Examples of the flame retardant aid include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide. Examples of the filler include silica, talc, clay, mica, titanium oxide, glass beads, glass flake, glass fiber, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium silicate, potassium titanate, aluminum borate, boric acid. Examples thereof include magnesium and carbon fiber. Other additives include, for example, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity-imparting agents, mold release agents, lubricants, dyes, and A pigment etc. can be mentioned. One or more of these other components may be contained in the flame retardant resin composition.

(Flame-retardant masterbatch production method)
The flame retardant masterbatch can be produced by melt-kneading a polyolefin-based resin, a first flame retardant, a second flame retardant, a compatibilizing agent, and other components blended as necessary. The method of melt kneading is not particularly limited, and a known melt kneading method can be employed. As specific examples, each component is mixed in advance using various mixers such as a high-speed mixer such as a tumbler or a Henschel mixer, and then Banbury mixer, roll, plastograph, single screw extruder, twin screw extruder, and A method of melt kneading with a kneader such as a kneader can be mentioned. Among these, since production efficiency is good, a production method in which melt-kneading is performed using an extruder is preferable, and a production method using a twin-screw extruder is more preferable. Each component is melt-kneaded using an extruder, the kneaded product is extruded into a strand shape, and then the kneaded product extruded into a strand shape can be processed into a pellet form or a flake form. In addition, the form of the masterbatch is preferably a granular form, a tabred form, a pellet form, a flake form, and a fiber form, and more preferably a pellet form.

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

<Flame-retardant resin composition>
A flame retardant masterbatch is intended to impart flame retardancy to a thermoplastic resin that constitutes all or part of a flame retardant product, that is, a thermoplastic resin to which flame retardancy is to be imparted. It is a component added to. That is, the flame retardant resin composition of the present invention is a resin composition for molding a flame-retardant molded article (product) containing a thermoplastic resin and the above-mentioned flame retardant master batch. Here, the “resin composition for molding a flame-retardant molded product (product)” means that the flame-retardant resin composition is molded as all or part of the flame-retardant molded product (product). It refers to a composition that can be used as it is for molding.

  As the thermoplastic resin, a polyolefin-based resin is preferable, similarly to the resin component that is the base material of the flame-retardant masterbatch. Among these, a polyolefin resin of the same type as the resin component that is the base material in the flame-retardant masterbatch is more preferable. In addition, as a form of a flame retardant resin composition, a powder form, a granular form, a tablet (tablet) form, a pellet form, flake form, a fiber form, liquid form etc. can be mentioned, for example.

  The content of the first flame retardant in the flame retardant resin composition is preferably 0.2 to 3% by mass, more preferably 0.3 to 2.5% by mass, It is especially preferable that it is -2 mass%. If the content of the first flame retardant is less than 0.2% by mass, the flame retardancy of the obtained molded product may be slightly insufficient. On the other hand, if the content of the first flame retardant is more than 3% by mass, the workability may be slightly lowered.

  The content of the second flame retardant in the flame retardant resin composition is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.7% by mass, and 0.15%. It is especially preferable that it is -0.5 mass%. When the content of the second flame retardant is less than 0.05% by mass, the flame retardancy of the obtained molded product may be slightly insufficient. On the other hand, if the content of the second flame retardant is more than 1% by mass, odor may easily remain in the molded product (molded product).

  The content of the compatibilizer in the flame retardant resin composition is preferably 0.1 to 2% by mass, more preferably 0.3 to 1.5% by mass, and 0.45 to 1 It is particularly preferable that the content is% by mass. If the content of the compatibilizer is less than 0.1% by mass, the bleed phenomenon may be somewhat likely to occur. On the other hand, if the content of the compatibilizer is more than 2% by mass, the flame retardancy may be slightly insufficient. In addition, since the excess compatibilizer tends to bleed out, the machine base such as a spinning machine may be contaminated, and it may be disadvantageous in terms of cost.

  When molding a molded product having flame retardancy, it is better to add the previously prepared flame retardant masterbatch rather than directly adding the flame retardant to the thermoplastic resin to which flame retardancy is to be imparted. In addition, components such as flame retardants are less likely to scatter, and it is difficult to contaminate molding machines such as extrusion molding machines and injection molding machines, which is preferable in terms of improving workability. Moreover, the flame-retardant resin composition desired can be easily prepared by using a flame-retardant masterbatch. For this reason, the flame-retardant resin composition with an economical advantage which can respond to low-cost production at low cost can be obtained.

<Molded product>
The molded article of the present invention is composed of the above-mentioned flame retardant resin composition. That is, a molded article having flame retardancy can be produced by molding the flame retardant resin composition of the present invention. A molded product can be manufactured by melting the flame retardant resin composition in various molding machines and then molding it. The molding technique can be appropriately selected according to the form and use of the molded product. Examples of the molding method include injection molding, extrusion molding, compression molding, blow molding, calendar molding, and inflation molding. Moreover, secondary molding such as vacuum molding or pressure molding can be performed on a sheet-like or film-like molded product obtained by extrusion molding, calendar molding, or the like.

  Specific examples of molded products include electrical and electronic parts, electrical parts, exterior parts, interior parts, etc., as well as various packaging materials, household goods, office supplies, piping, and agricultural materials in the fields of home appliances and automobiles. Can be mentioned. In particular, the above-mentioned flame retardant resin composition is suitable for uses molded into a film-like resin, a sheet-like resin, and a fibrous resin from the viewpoint of the flame-retardant effect. More preferred are films, sheets, fibers and the like.

  As described above, the flame retardant resin composition used as a molding raw material of the molded product of the present invention is obtained by using a flame retardant masterbatch which is less likely to generate unpleasant odor during production and has excellent processability. is there. For this reason, an unpleasant odor is unlikely to occur when the flame retardant resin composition is molded. Therefore, the molded article of the present invention can be suitably employed for applications used in a closed space such as indoors or vehicle interior materials.

  Hereinafter, although this invention is demonstrated concretely based on a test example, this invention is not limited to these test examples.

<Materials used>
In this test example, the following first flame retardant and second flame retardant and compatibilizers A to E were used. Moreover, the polypropylene resin A shown below was used as polyolefin resin.

(First flame retardant)
A phosphorus-based flame retardant represented by the following formula (1) (trade name “Nonen 73”, manufactured by Maruhishi Oil Chemical Co., Ltd.) was used as the “first flame retardant”.

(Second flame retardant)
A nitrogen-based flame retardant represented by the following formulas (2) and (3) (trade name “Flamestab NOR116”, manufactured by BASF, molecular weight: 2261 g / mol) was used as the “second flame retardant”. R in the following formula (2) is a group represented by the following formula (3), and (*) in the following formula (3) represents N and R in the following formula (2) are bonded to each other. Represents the bond of. About this flame retardant, it heats with the temperature increase rate of 10 degree-C / min from room temperature (25 degreeC) with the differential thermal analyzer (TG-DSC, brand name "TG-8110", the Rigaku company make), and a thermal characteristic. Was analyzed. As a result, it was found that the decomposition start temperature of this flame retardant was about 230 ° C.

(Compatibilizer A)
A NO-polyethylene wax type hindered amine compound (trade name “Hostavin Now”, manufactured by Clariant Chemicals) represented by the following formula (4-1) (where m represents an integer of 15 to 18) Used as “Solubilizer A”. This hindered amine compound is [reaction product of 4- (alkanoyl (C15-18) oxy) -2,2,6,6-tetramethylpiperidin-1-yloxyl and polyethylene wax]. In the following formula (4-1), the number of carbon atoms of the long-chain branched alkyl group derived from polyethylene wax is omitted. About this hindered amine type compound, it heated on the conditions of the temperature increase rate of 10 degree-C / min from room temperature (25 degreeC) with the differential thermal analyzer (TG-DSC, brand name "TG-8110", Rigaku Corporation make) The characteristics were analyzed. As a result, it was found that the decomposition initiation temperature of this hindered amine compound was about 260 ° C. Further, for this hindered amine compound, MALDI-TOFMS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometer, trade name “autoflex speed”, manufactured by Bruker) was used as its matrix material, DCTB (trans-2- [ The average molecular weight was measured using 3- (4-tert-butylphenyl) -2-methyl-2-propenylidene] malononitrile). As a result, it was found that the average molecular weight of the hindered amine compound was in the range of 2,500 to 3,400.

(Compatibilizer B)
A NO-R type hindered amine compound (trade name “ADK STAB LA-81”, manufactured by ADEKA) represented by the following formula (5-1) was used as “Compatibilizer B”.

(Compatibilizer C)
A polyolefin-based adhesive resin (trade name “Modic A515”, manufactured by Mitsubishi Chemical Corporation) having a structure in which the main chain is polyolefin and the EVA compound is bonded to the side chain was used as “Compatibilizer C”.

(Compatibilizer D)
A polyolefin resin having a structure in which the main chain is a polyolefin and a styrene compound is bonded to a side chain (trade name “Modiper A1100”, manufactured by NOF Corporation) was used as “Compatibilizer D”.

(Compatibilizer E)
An acid-modified polyolefin resin (trade name “YUMEX 1001”, manufactured by Sanyo Kasei Co., Ltd.) having a structure in which the main chain is a polyolefin and a carboxylic anhydride having a polar group is bonded to a side chain is a compatibilizer E ".

(Polypropylene (PP) resin)
Powdery polypropylene resin A (trade name “J105P”, manufactured by Prime Polymer Co., Ltd.) was used as “polypropylene (PP) resin”.

<Manufacture of master batch>
(Test Example 1)
70 parts by mass of polypropylene resin, 20 parts by mass of the first flame retardant, and 10 parts by mass of the compatibilizer A were blended and mixed thoroughly using a Henschel mixer to obtain a mixture. The mixture obtained using a twin screw extruder was kneaded at a temperature of 230 ° C., and the kneaded product was extruded into a strand shape. The kneaded product extruded in a strand form was cooled with water and then processed using a pelletizer to produce a pellet-like master batch 1.

(Test Examples 2 to 12)
Except having set it as the mixing | blending (unit: mass part) shown in Table 1, it carried out similarly to the above-mentioned Test example 1, and manufactured the pellet-shaped masterbatch 2-12.

<Evaluation of master batch>
(Processability)
The state of occurrence of sticking of the melt to the screw of the twin screw extruder during the production of the master batch was confirmed, and the workability of the master batch was evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: The twin screw extruder could be operated satisfactorily with almost no melt adhering to the screw of the twin screw extruder.
Δ: Slight adhesion of the melt to the screw of the twin screw extruder was confirmed, but a master batch could be produced.
X: The melt was fixed and wound around the screw of the twin screw extruder, and the operation of the twin screw extruder was difficult.

(Work environment)
It was confirmed whether or not an unpleasant odor was generated during the production of the masterbatch, and the working environment was evaluated according to the following evaluation criteria. The results are shown in Table 1.
○: Almost no odor was felt.
Δ: Slight odor generation was felt, but no odor that would make working difficult was felt.
X: Odor which felt clearly was generated.

(Compatibility)
The generation | occurrence | production state of the bleed thing to the water tank at the time of masterbatch manufacture was confirmed, and the compatibility with a flame retardant and resin was evaluated according to the evaluation criteria shown below. The results are shown in Table 1.
◯: A master batch having good compatibility could be produced with almost no bleeding being generated in the water tank.
Δ: Generation of bleed material was confirmed in the water tank, but since the generated bleed material was a small amount, a masterbatch with a moderate compatibility could be produced.
X: Since generation | occurrence | production of a large amount of bleed material was confirmed in the water tank, although the compatibility was not so good, the masterbatch was able to be manufactured.

<Manufacture of flame retardant evaluation specimen>
(Test Examples 13 to 17)
About each of the master batches 3-5, 8, and 12 manufactured by the above-mentioned test examples 3-5, 8, and 12, the flame-retardant resin composition which assumed the composition at the time of manufacturing a product was prepared. Specifically, each masterbatch and the same polypropylene resin as the polypropylene resin used in the masterbatch were dry blended to prepare a flame retardant resin composition for molding a test specimen. At this time, the total flame retardant content in the flame retardant resin composition was adjusted to 1.4% by mass. In addition, since the compatibilizer A and the compatibilizer B are components that exhibit an action as a flame retardant, the content of these components was also included in the “flame retardant” and calculated. The composition of the prepared flame retardant resin composition is shown in Table 2 (unit: mass%).

  The flame retardant resin composition was spun using a spinning machine to produce a 5 denier yarn. The produced yarn was bundled and a force as uniform as possible was applied to produce a torsion bar having a length of 20 cm. The torsion bar manufactured in this way was used as a test body for flame retardancy evaluation.

<Flame resistance test (measurement of flame contact number)>
In accordance with JIS L1091: 1999 “Flammability Test Method for Textile Products” Method D (flame contact test), the number of flame contacts was measured using the torsion bar produced as a test specimen. Specifically, the number of times of flame contact (N = 5 average) required until the 20 cm specimen was burned out was measured. The measurement results are shown in Table 2. In addition, in the present Example, the thing whose flame contact frequency was 2.7 or more was evaluated as "pass".

  If the flame-retardant masterbatch of this invention is used, the flame retardance of various molded articles, such as a fiber, can be improved effectively.

Claims (6)

Containing a polyolefin-based resin, a first flame retardant represented by the following formula (1), a second flame retardant represented by the following formulas (2) and (3), and a compatibilizing agent:
The compatibilizer is at least one of a hindered amine compound represented by the following general formula (4) and a hindered amine compound represented by the following general formula (5):
The content of the first flame retardant is 7 to 18% by mass,
A flame retardant master batch in which the content of the second flame retardant is 5% by mass or less.

(R in the formula (2) is a group represented by the formula (3), and (*) in the formula (3) is N to which R in the formula (2) is bonded. Represents a bond with

(In the general formula (4), R ₁ represents an alkyl group derived from a polyolefin wax, and R ₂ represents an optionally substituted alkyl group having 1 to 20 carbon atoms)

(In the general formula (5), R ₃ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, n represents an integer of 2 to 4, and R ₄ represents n in parentheses. Represents an optionally substituted divalent to tetravalent acyl group to which   The flame-retardant masterbatch according to claim 1, wherein the content of the compatibilizer is 1 to 10% by mass. The flame retardant masterbatch according to claim 1 or 2, wherein the compatibilizer is at least one of a compound represented by the following formula (4-1) and a compound represented by the following formula (5-1). .

  The flame-retardant resin composition containing a thermoplastic resin and the flame-retardant masterbatch as described in any one of Claims 1-3.   A molded article comprising the flame retardant resin composition according to claim 4.   The molded article according to claim 5, which is a film, a sheet, or a fiber.