JP2015189785A - Flame-retardant soft resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant soft resin composition which does not cause deterioration of flexibility and mechanical properties when added with a flame retardant, or emission of harmful gases, e.g. halogen gases, and allows formation of a molding of a low specific gravity with good moldability and a molding using it.SOLUTION: A resin composition contains 0.1-200 pts. mass of a non-halogen flame retardant other than metal hydroxides to 100 pts. mass of a resin, and the resin contains a polyolefin resin. A molding using it is also provided.

Description

  The present invention relates to a flame retardant soft resin composition. More specifically, a flame retardant soft resin composition excellent in flame retardancy, flexibility, and mechanical properties, generating no harmful gas such as halogen gas, and having a low specific gravity and good moldability, and the same The present invention relates to a molded body using

Conventionally, many soft resins have been used for automobile parts, packaging materials, agricultural materials, home appliances, packing materials for building materials, and the like. In particular, polyvinyl chloride is used as a soft resin excellent in mechanical properties, flexibility, and flame retardancy. Polyvinyl chloride generates harmful and corrosive halogen gas during combustion, so there are a number of problems such as corrosion of equipment and suction damage during fire evacuation. Substitution is progressing.
However, since the thermoplastic elastomer is very flammable, it is made flame retardant by adding a flame retardant. Examples of the flame retardant used for making the thermoplastic elastomer flame retardant include a brominated flame retardant and antimony trioxide, or a metal hydroxide.

  For example, in Patent Document 1, a mechanical component containing a thermoplastic polyester elastomer, a styrenic block copolymer modified with a functional group, a resin component mixed with polypropylene in a specific ratio, a brominated flame retardant, and antimony trioxide. A resin composition that covers a flame-retardant optical fiber core that has excellent characteristics and flame retardancy, has adhesion to an optical fiber, and can withstand use under high temperature and high humidity has been disclosed. In Patent Document 2, as a non-halogen flame retardant resin composition having a softness equivalent to that of a halogen-based material, an ethylene-vinyl acetate copolymer, a crystalline polyolefin-based resin, and a metal hydroxide are included in a specific ratio. And a non-halogen flame retardant thermoplastic elastomer composition in which the ethylene-vinyl acetate copolymer is silane-crosslinked. In Patent Document 3, as a flame retardant resin composition that is excellent in flame retardancy, tensile properties, and moldability and does not whiten even when bent, a specific block copolymer, softener for non-aromatic rubber, metal hydroxide A flame retardant thermoplastic elastomer resin composition for covering an electric wire comprising a flame retardant containing a product, a peroxide-crosslinked olefin resin and a peroxide-decomposable olefin resin is disclosed.

JP 2004-18300 A JP 2008-31354 A JP 2008-226850 A

  However, flame retardants using brominated flame retardants and antimony trioxide have the problem of generating harmful and corrosive halogen gases during combustion. In addition, in order to obtain the desired flame retardancy, it is necessary to add a large amount of metal hydroxide, extremely impairing mechanical properties and flexibility, and high specific gravity. Become.

  Therefore, the present invention does not cause deterioration of flexibility and mechanical properties even when a flame retardant is added, does not generate a harmful gas such as halogen gas, and has a low specific gravity and can obtain a molded product with good moldability. It is an object to provide a soft resin composition and a molded body.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a resin composition containing a non-halogen flame retardant excluding metal hydroxide in a specific amount relative to a polyolefin resin. .
That is, this invention relates to the following flame-retardant soft resin composition.

1. A resin composition containing 0.1 to 200 parts by mass of a non-halogen flame retardant excluding metal hydroxide with respect to 100 parts by mass of the resin, wherein the resin contains at least a polyolefin resin. object.
2. 2. The flame-retardant soft resin composition according to 1 above, wherein the resin is a mixed resin containing a polyolefin-based resin and a thermoplastic elastomer.
3. 2. The flame-retardant soft resin composition according to 1, wherein the resin contains a polyolefin-based resin and a thermoplastic elastomer at a mass ratio of 100: 0 to 1:99.
4). 4. The flame retardant soft resin composition according to any one of 1 to 3, wherein the polyolefin resin is one or more selected from a polypropylene resin and a polyethylene resin.
5. 5. The flame retardant soft resin composition according to any one of 2 to 4, wherein the thermoplastic elastomer is one or more selected from olefin elastomers and styrene elastomers.
6). The non-halogen flame retardant is one or more selected from phosphate compounds and derivatives thereof, phosphate esters and derivatives thereof, red phosphorus, NOR type hindered amine compounds and derivatives thereof, and sulfates and derivatives thereof. The flame-retardant soft resin composition according to any one of 1 to 5 above.
7). The flame-retardant soft resin composition according to any one of 1 to 6 above, wherein a molded product having a type A durometer hardness of 95 or less according to JIS K6253 is obtained.
8). The molded object obtained by injection-molding the flame-retardant soft resin composition in any one of said 1-7.
9. The molded object obtained by extruding the flame-retardant soft resin composition in any one of said 1-7.
10. The laminated structure which has at least 1 layer which consists of a flame-retardant soft resin composition in any one of said 1-7.
11. The pellet obtained from the flame-retardant soft resin composition in any one of said 1-7.

  According to the present invention, flame retardancy that is excellent in flame retardancy, flexibility, and mechanical properties (tensile properties), does not generate harmful gases such as halogen gas, and can obtain a molded product with low specific gravity and good moldability. A soft resin composition and a molded body can be provided.

[resin]
The resin contained in the flame-retardant soft resin composition of the present invention only needs to contain at least a polyolefin resin, and a polyolefin resin may be used alone as the resin. Moreover, you may use the mixed resin containing polyolefin resin and a thermoplastic elastomer as said resin.
The method for mixing the polyolefin resin and the thermoplastic elastomer is not particularly limited. For example, mixing involving copolymerization or mixing by melt kneading may be used.

(Polyolefin resin)
As the polyolefin resin, for example, a polypropylene resin, a polyethylene resin, a polybutene resin, a polypentene resin, or the like can be used. Among these, from the viewpoints of moldability, low specific gravity, and chemical resistance, the polyolefin resin is preferably a resin containing one or more selected from polypropylene resins and polyethylene resins.
When this polyolefin resin contains two or more kinds of polyolefin resins, the mixing method is not particularly limited. For example, mixing involving copolymerization or mixing by melt kneading may be used.

As a polypropylene resin, it can be comprised by 1 type, or 2 or more types chosen from the homopolymer of propylene, the copolymer which has a propylene as a main component, etc.
Although there is no restriction | limiting in particular as a homopolymer of propylene, From the viewpoint of making it lightweight and excellent in a moldability, the propylene single weight whose melt mass flow rate in 230 degreeC and load 2.16kg is 0.1-200 g / 10min. From the viewpoint of mechanical properties of the resin composition, it is more preferable that the melt mass flow rate at 230 ° C. and a load of 2.16 kg is 0.2 to 60 g / 10 min.

Examples of the copolymer having propylene as a main component include, for example, a random copolymer of one or more α-olefins other than propylene and propylene, and one or two or more types other than propylene and propylene. And a block copolymer with an α-olefin. Among copolymers mainly composed of propylene, a propylene copolymer having a melt mass flow rate of 0.1 to 200 g / 10 min at 230 ° C. and a load of 2.16 kg from the viewpoint of light weight and excellent moldability. Further, from the viewpoint of mechanical properties of the resin composition, the melt mass flow rate at 230 ° C. and a load of 2.16 kg is more preferably 0.2 to 60 g / 10 minutes.
Examples of α-olefins other than propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned.

As a polyethylene-type resin, it can be comprised by 1 type, or 2 or more types chosen from the homopolymer of ethylene, the copolymer which has ethylene as a main component, etc.
Examples of the homopolymer of ethylene include low-density polyethylene, linear low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. From the viewpoint of light weight and excellent moldability, the density is 0.910. An ethylene homopolymer having a melt mass flow rate of 0.01 to 200 g / 10 min at ˜0.965 g / cm ³ , 190 ° C. and a load of 2.16 kg is preferred. If the melt mass flow rate at 190 ° C. and a load of 2.16 kg is within the above range, there is no risk of problems in the fluidity of the resin composition and the surface appearance of the molded article, and it is 0.01 to 60 g / 10 min. Is more preferable.

Examples of the copolymer containing ethylene as a main component include, for example, a random copolymer of one or more α-olefins other than ethylene and ethylene, and one or more of other than ethylene and ethylene. And a block copolymer with an α-olefin. Among copolymers containing ethylene as a main component, an ethylene copolymer having a melt mass flow rate of 0.01 to 200 g / 10 min at 190 ° C. and a load of 2.16 kg from the viewpoint of light weight and excellent moldability. Is preferred. Moreover, if the melt mass flow rate at 190 ° C. and a load of 2.16 kg is within the above range, there is no risk of problems in the fluidity of the resin composition and the surface appearance of the molded body, and 0.01 to 60 g / 10 min. More preferably.
Examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned.

(Thermoplastic elastomer)
Although it does not specifically limit as a thermoplastic elastomer, An olefin-type elastomer and a styrene-type elastomer are mentioned, These may be used individually by 1 type and may be used in combination of 2 or more type.
Among thermoplastic elastomers, it is preferable that the melt mass flow rate at 230 ° C. and a load of 2.16 kg is 0.1 to 200 g / 10 min from the viewpoint of excellent flexibility, molding processability and mechanical properties. From the viewpoint of mechanical properties of the resin composition, the melt mass flow rate at 230 ° C. and a load of 2.16 kg is more preferably 0.2 to 60 g / 10 min.

Examples of the olefin elastomer include elastomers obtained by copolymerization of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, and 1-octene, and styrene monomers or non-conjugated dienes. And an elastomer obtained by copolymerization of Examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene.
Specifically, ethylene-propylene copolymer elastomer, ethylene-1-butene copolymer elastomer, ethylene-propylene-1-butene copolymer elastomer, ethylene-1-hexene copolymer elastomer, ethylene-1-octene Copolymer elastomer, ethylene-styrene copolymer elastomer, ethylene-norbornene copolymer elastomer, propylene-1-butene copolymer elastomer, ethylene-propylene-nonconjugated diene copolymer elastomer, ethylene-1-butene-non Examples include amorphous elastic copolymers mainly composed of olefins such as conjugated diene copolymer elastomers and ethylene-propylene-1-butene-nonconjugated diene copolymer elastomers, derivatives thereof, and acid-modified derivatives. it can. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the olefin elastomer include compound type TPO (“TPO” means olefin thermoplastic elastomer) and reactor TPO (R-TPO). These may be used individually by 1 type and may be used in combination of 2 or more type. Compound type TPO is obtained by polymerizing resin and rubber separately and compounding at least two components obtained by the polymerization. The reactor TPO is also referred to as a polymerization reactor TPO, and is an olefin-based thermoplastic elastomer in which a rubber component as a soft part is dispersed in a matrix resin that is a hard part during polymerization.

Examples of the styrene elastomer include a block copolymer of a styrene compound and a conjugated diene compound, a random copolymer, and a hydrogenated product thereof. Examples of the styrene compound include alkyl styrene such as styrene, α-methyl styrene, p-methyl styrene, and pt-butyl styrene, p-methoxy styrene, and vinyl naphthalene. Examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadiene. The molecular structure of these styrenic thermoplastic elastomers may be any of linear, branched, radial, and combinations thereof.
Specifically, styrene-butadiene block copolymer (SBR), styrene-butadiene-styrene triblock copolymer (SBS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-ethylene-butylene.・ Ethylene block copolymer (SEBC) styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer (SIS), styrene-isoprene rubber (SIR), styrene-ethylene-propylene-styrene block copolymer (SEPS), polystyrene-poly (ethylene / butylene) block copolymer, polystyrene-poly (ethylene / propylene) block copolymer, styrene-ethylene-butylene-ethylene block copolymer, and hydrogenation or acid modification thereof did Conductor, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

(Mixing ratio)
The mixing ratio of the polyolefin-based resin and the thermoplastic elastomer is preferably 100: 0 to 1:99 in terms of mass ratio, and from the viewpoint of flexibility and molding processability of the resin composition, 5:95 to 95. : 5 is more preferable, and 30:70 to 70:30 is even more preferable.

[Non-halogen flame retardant]
The halogen-free flame retardant is not particularly limited as long as it is not a metal hydroxide, but from the viewpoint of flame retardancy, specific gravity, and moldability of the resin composition, phosphate compounds and derivatives thereof, red phosphorus, NOR type hindered amines. It is preferable that it is 1 type, or 2 or more types chosen from a compound and its derivative (s), phosphate ester and its derivative, and sulfate and its derivative (s).

  Examples of the phosphate compound include, for example, ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, melamine orthophosphate, Examples thereof include calcium phosphate and magnesium phosphate, and derivatives or mixtures thereof. A phosphate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The NOR type hindered amine compound is a known compound in JP-A-11-80569, JP-A-2001-348724, JP-A-2007-56090, and the like, and is sometimes referred to as a NOR-type HALS stabilizer.
As the NOR type hindered amine compound, for example, a compound represented by the following formula (1) can be used.

In said formula (1), R < ¹ > -R < ⁴ > represents a hydrogen atom or the organic group of following formula (2), respectively. At least one of R ^{1 to} R ⁴ is an organic group of the following formula (2).

In the formula, R ⁵ represents an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group or a phenylalkyl group having 7 to 15 carbon atoms, and R ⁶ , R ⁷ , R ⁸ and R ⁹ represents an alkyl group having 1 to 4 carbon atoms. R ¹⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.
Of the alkyl groups having 1 to 17 carbon atoms which are R ⁵ , a methyl group or an octyl group is preferable. Of the cycloalkyl groups having 5 to 10 carbon atoms, a cyclohexyl group is preferred. Moreover, a phenyl group is preferable among a phenyl group or a C7-15 phenylalkyl group.
Of the alkyl groups having 1 to 4 carbon atoms which are R ^{6 to} R ⁹ , a methyl group is preferable.
Of the linear or branched alkyl groups having 1 to 12 carbon atoms which are R ¹⁰ , an n-butyl group is preferable.
In formula (1), those in which R ¹ , R ² and R ³ are organic groups of formula (2), or those in which R ¹ , R ² and R ⁴ are organic groups of formula (2) are preferred. .

As the NOR type hindered amine compound, specifically, N, N ′, N ′ ″-tris {2,4-bis [(1-hydrocarboxy-2,2,6,6-tetramethylpiperidine-4- Yl) alkylamino] -s-triazin-6-yl} -3,3′-ethylenediiminodipropylamine, N, N ′, N ″ -tris {2,4-bis [(1-hydrocarboxy) -2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine and its crosslinked derivatives, bis (1 -Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1 -Cyclohe Siloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate and bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and 1-cyclohexyl And oxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate.
NOR type hindered amine compounds may be used alone or in combination of two or more.

  Examples of the phosphoric acid ester and derivatives thereof include the following compound Nos. 1-Compound No. 1 6, and derivatives thereof, mixtures thereof and the like. Phosphoric acid esters and derivatives thereof may be used alone or in combination of two or more.

  Examples of the sulfates and derivatives thereof include melamine sulfate, guanidine sulfate, guanylurea sulfate, and combinations thereof, and derivatives and mixtures thereof. A sulfate and its derivative may be used individually by 1 type, and may be used in combination of 2 or more type.

(Content ratio)
In the flame retardant soft resin composition of the present invention, the content ratio of the non-halogen flame retardant is 0.1 to 200 parts by mass, preferably 0.5 to 150 parts by mass with respect to 100 parts by mass of the resin. More preferably, it is 1-100 mass parts. When the content ratio of the non-halogen flame retardant is less than 0.1 parts by mass, flame retardancy is not exhibited. Moreover, when it exceeds 200 mass parts, a moldability fall, the fall of a molded object surface external appearance, and specific gravity will become high.

[Additive component]
The flame retardant soft resin composition of the present invention may further contain various additives as necessary. Examples of additives include flame retardant aids, ultraviolet absorbers, light stabilizers, antioxidants, lubricants, crystal nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial / antifungal agents, and pigments. Etc. The content of the additive is not particularly limited as long as the properties of the resin composition are not impaired.

The flame retardant aid can be used to further improve the flame retardancy of the resin composition depending on the application.
Examples of flame retardant aids include, for example, zinc borate, polytetrafluoroethylene, metal oxide, silicon dioxide hydrotalcite, magnesium bicarbonate, antimony trioxide, zinc oxide, aluminum oxide, magnesium oxide, silicon oxide, zirconium oxide, Examples thereof include vanadium oxide, molybdenum oxide and its surface-treated product, pentaerythritol, dipentaerythritol, tripentaerythritol, monopentaerythritol, tris (2-hydroxyethyl) isocyanurate, and polytetrafluoroethylene. These may be used individually by 1 type and may be used in combination of 2 or more type.

The ultraviolet absorber is a component that absorbs ultraviolet rays that promote deterioration of the resin component, and is not particularly limited, and examples thereof include benzophenone compounds, triazole compounds, and benzoate compounds.
Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone) and the like 2 -Hydroxybenzophenones; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazo- 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazol, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazol 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6- 2- (2′-hydroxyphenyl) benzotriazoles such as benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol Monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; Ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-me Cyanoacrylates such as xylphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, 2- (2-hydroxy -4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-ditert-butylphenyl) And triaryltriazines such as -s-triazine. These may be used individually by 1 type and may be used in combination of 2 or more type.

The light stabilizer is a component that takes in radicals that promote deterioration of the resin component, and is not particularly limited, and examples thereof include an NH type hindered amine compound and an N-methyl type hindered amine compound.
Specifically, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl -4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1, 2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bi (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl- 4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4- Piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8, 12-tetrakis [ , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl)] Amino) -s-triazin-6-yl] aminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) ) Amino) -s-triazin-6-yl] hinder doors such as aminoundecane And the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
In addition, although an ultraviolet absorber and a light stabilizer may each be used independently and may be mixed and used, it is preferable to mix and use from a viewpoint that deterioration of a resin component can be prevented more.

Although it does not specifically limit as antioxidant, A phenolic antioxidant, phosphorus antioxidant, thioether type antioxidant, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
Specific examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl). -4-hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m -Cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6- Tributyl-m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) ) Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert Tributyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [ 3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] Terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane , Triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of phosphorus antioxidants include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methyl. Phenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4 -Ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) penta Erythritol diphosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; pentaerythritol tetra (β-alkylmercaptopropionic acid) Examples include esters, etc. These may be used alone or in combination of two or more.

The lubricant is not particularly limited, and examples thereof include fatty acid amide lubricants, fatty acid ester lubricants, fatty acid lubricants, and fatty acid metal salt lubricants. These may be used individually by 1 type and may be used in combination of 2 or more type.
Specific examples of the aliphatic amide lubricant include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene biserucic acid amide, and ethylene bis lauryl. Examples include acid amides. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the aliphatic ester lubricant include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, myristic Isopropyl acid, isopropyl palmitate, octyl palmitate, octyl palm fatty acid octyl stearate, beef tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, linear C28-30 Unbranched saturated monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerin ester, montanic acid and butylene glycol ester, montanic acid and trimethylol eta Ester, montanic acid and trimethylolpropane ester, montanic acid and pentaerythritol ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan trioleate, polyoxy Examples include ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the fatty acid lubricants, specific examples of saturated fatty acids include lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid) ), Stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), serotic acid (Hexadocosanoic acid), montanic acid (octadocosanoic acid), melicic acid, etc. are mentioned, and lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid are particularly mentioned.

Among the fatty acid lubricants, unsaturated fatty acids include myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid), ricinoleic acid (Octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid (9,11, 13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), nervonic acid (tetradocosanoic acid) and the like.
One of these fatty acid-based lubricants may be used alone, or two or more thereof may be used in combination.
Examples of the fatty acid metal salt lubricant include lithium salt, calcium salt, magnesium salt and aluminum salt of the fatty acid of the fatty acid lubricant. These may be used individually by 1 type and may be used in combination of 2 or more type.

The crystal nucleating agent is not particularly limited, and examples thereof include sorbitols, phosphorus nucleating agents, rosins, and petroleum resins.
Specifically, sorbitols such as alkyl-substituted benzylidene sorbitol (1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, 1,3-o- Methylbenzylidene 2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-dimethylbenzylidene) Sorbitol, etc.), phosphorus nucleating agents (bis (4-t-butylphenyl) sodium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, organic phosphate Composite products, etc.), sodium benzoate, aluminum pt-butylbenzoate, sodium montanate, calcium montanate, aluminum oxide, kaolin Leh, talc, rosin, petroleum resins, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The softening agent is not particularly limited, and examples thereof include liquid paraffin, mineral oil softener (process oil), and non-aromatic rubber mineral oil softener (process oil). These may be used individually by 1 type and may be used in combination of 2 or more type.

The antistatic agent is not particularly limited, and examples thereof include cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, and fatty acid partial esters such as glycerin fatty acid monoesters.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate , (3-laurylamidopropyl) trimethylammonium methylsulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate Alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salt, alkyl phosphate ester salt, alkyl phosphate amine salt, monoglyceride stearate , Pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol Examples thereof include monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, and hydroxyethyl imidazoline sulfate. These may be used individually by 1 type and may be used in combination of 2 or more type.

Although it does not specifically limit as a metal deactivator, A hydrazine type metal deactivator, a nitrogen compound type metal deactivator, a phosphite ester type metal deactivator, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of hydrazine-based metal deactivators include N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, Examples include decanedicarboxylic acid disalicyloylbidrazide, oxalic acid bisbenzylidenehydrazide, and the like.
Nitrogen-based metal deactivators include N, N′-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4, -triazole, acid amide metal deactivator, melamine and the like.
Phosphite-based metal deactivators include tris [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5-t-butyl) phenyl-5-methyl] phosphite, etc. Is mentioned.
These metal deactivators may be used individually by 1 type, and may be used in combination of 2 or more type.

The antibacterial / antifungal agent is not particularly limited, and examples thereof include an organic compound antibacterial / antifungal agent, a natural organic antibacterial / antifungal agent, and an inorganic antibacterial / antifungal agent. These may be used individually by 1 type and may be used in combination of 2 or more type.
Organic compound antibacterial / antifungal agents include thiabendazole, 2-n-octyl-4-isothiazolin-3-one, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, N- (fluorocyclomethylthio)- Phthalimide, bis (1-hydroxy-2 (1H) pyridinethionate-O, S) zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 10,10′-oxybisphenoxyarsine Etc.
Examples of natural organic antibacterial and antifungal agents include allyl isothiocyanate.
Inorganic antibacterial / antifungal agents include silver-supported silica gel, silver-supported zeolite, silver ions-supported hydroxyapatite, silver ions-supported water glass, silver ions-supported zirconium phosphate, and silver ions. Examples include supported ammonium polyphosphate, zeolite supporting silver and copper ions, and zeolite supporting zinc.
One of these antibacterial / antifungal agents may be used alone, or two or more thereof may be used in combination.

Although it does not specifically limit as a pigment, An inorganic pigment, an organic pigment, etc. are mentioned.
Inorganic pigments include titanium oxide, bengara, alumina white, yellow iron oxide, cadmium red, vermilion, yellow lead, molybdate orange, gypsum, barium sulfate, calcium carbonate, lead white, ultramarine, manganese violet, cobalt violet, emerald green. , Bitumen, carbon black, aluminum powder, zinc powder and the like.
Examples of organic pigments include azo pigments, acidic dye lakes, basic dye lakes, and condensed polycyclic pigments.
These pigments may be used alone or in combination of two or more.

[Kneading / Molding]
Although the flame-retardant soft resin composition of the present invention is not particularly limited, for example, each raw material can be melt-kneaded and prepared as pellets with a pelletizer. The compounding and kneading at this time are premixed with a commonly used equipment such as a ribbon blender, a drum tumbler, etc., Henschel mixer (trade name), Banbury mixer, single screw extruder, twin screw extruder, It can be performed by a method using a multi-screw extruder, a kneader or the like.
What is necessary is just to select the heating temperature in the case of kneading | mixing suitably in the range of 130-250 degreeC normally.

The flame-retardant soft resin composition of the present invention is the above-described melt-kneading molding machine, or using the obtained pellet-shaped resin composition as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, Various molded bodies can be produced by a press molding method, a vacuum molding method, a foam molding method, or the like. In particular, by the melt-kneading method, a molding raw material that is a flame-retardant soft resin composition in the form of pellets is manufactured, and then the pellets are used to manufacture an injection-molded body by injection molding and an extrusion-molded body by extrusion molding. It can use suitably for manufacture. Moreover, after forming into an extrusion molded body such as an extruded sheet by extrusion molding, a molded body may be formed by processing or molding such as thermoforming.
Furthermore, it is good also as a laminated structure which makes it laminate | stack on the base shape | molded previously, or coextrudes a flame-retardant soft resin composition with other resin, and has at least one layer of the flame-retardant soft resin composition.

[Physical properties of resin composition]
(Flexibility)
The flame-retardant soft resin composition of the present invention can give a molded article having a flexibility with a type A durometer hardness of 95 or less based on JIS K6253. The hardness is preferably 45 to 90, more preferably 60 to 80, from the viewpoints of flexibility and mechanical properties.

(specific gravity)
The flame retardant soft resin composition of the present invention has a low specific gravity, and preferably has a specific gravity of 0.90 to 1.35 g / cm ³ from the viewpoint of weight reduction and moldability, and 0.91 to 1.30 g. / Cm ³ is more preferable. The specific gravity is specifically measured by the method described in the examples.

(Mechanical properties)
The flame-retardant soft resin composition of the present invention is excellent in tensile properties such as tensile elongation, tensile strength, and tensile modulus.
The tensile elongation of the flame retardant soft resin composition is preferably 200 to 1500% and more preferably 300 to 1200% from the viewpoint of elongation in the molded body. Specifically, the tensile elongation is measured by the method described in Examples.
The tensile strength of the flame retardant soft resin composition is preferably 3 to 35 MPa, more preferably 5 to 25 MPa, from the viewpoint of strength in the molded body. Specifically, the tensile elastic strength is measured by the method described in Examples.
The tensile elastic modulus of the flame retardant soft resin composition is preferably 10 to 500 MPa, more preferably 20 to 400 MPa, from the viewpoint of flexibility in the molded body. Specifically, the tensile elastic modulus is measured by the method described in Examples.

[Molded body]
The molded body of the present invention is formed by using a flame retardant soft resin composition obtained by blending the above-mentioned resin with a non-halogen flame retardant and, if necessary, various additives within a specific range. It is excellent in flammability, flexibility, and mechanical properties (tensile properties), does not generate harmful gas such as halogen gas, and can obtain a molded product with low specific gravity and good moldability.
Specifically, if the flame-retardant soft resin composition of the present invention is used, the molded article of the present invention can be molded by general injection molding or extrusion molding without requiring special equipment. Therefore, the molded body of the present invention can be suitably used for automobile parts, packaging materials, agricultural materials, home appliances, building material packing materials, and the like.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The performance test of the resin composition obtained in each example was performed as follows.
[performance test]
(1) Flexibility Using a test piece produced by the method described later, the surface hardness was measured and evaluated by a spring type hardness tester type A durometer in accordance with JIS K6253. The obtained results are shown in Table 1.
(2) Specific gravity It measured by the method based on specific gravity ASTM D792 using the test piece (size: 127 mm x 12.7 mm, thickness: 1.6 mm) produced by the below-mentioned method.
(3) Flame retardancy UL94 50W vertical combustion test (V test) using test piece a (size: 127 mm × 12.7 mm, thickness: 1.6 mm) produced by the method described later, or test piece b (size) The thickness was evaluated by a method based on a UL94 thin material vertical combustion test (VTM test) using 200 mm × 50 mm and thickness: 100 μm. In addition, what was outside the standards of UL94 is indicated as “Not V” or “Not VTM”. The obtained results are shown in Table 1.
(4) Tensile properties Using a test piece prepared by the method described below, the tensile elongation (%), tensile strength (MPa), and tensile modulus (MPa) were measured and evaluated by a method based on JIS K6251. . The obtained results are shown in Table 1.
(5) Formability The moldability was evaluated by injection moldability and extrusion molding. The obtained results are shown in Table 1.
・ Injection moldability Pellets produced by the method described below were produced by a molding machine having a cylinder temperature of 180 ° C., a mold temperature of 30 ° C., and an injection pressure of 80 MPa, and a spiral shaped product having a wall thickness of 2 mm and a width of 10 mm. The flow length (spiral flow) was measured.
Extrudability By measuring the melt tension using pellets produced by the method described later, the shapeability that is an index of the extrusion moldability was evaluated.

Moreover, each component used in each example is as follows.
(resin)
Polyolefin resin:
Polyethylene resin (A) [manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LJ902, low density polyethylene, density: 0.915 g / cm ³ , 190 ° C., melt mass flow rate at a load of 2.16 kg: 45 g / 10 min]
Polyethylene resin (B) [manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec HE30, low density polyethylene, density: 0.915 g / cm ³ , 190 ° C., melt mass flow rate at a load of 2.16 kg: 0.5 g / 10 Min)
-Polypropylene resin [manufactured by Nippon Polypro Co., Ltd., trade name: Wintech WFX6, propylene ethylene random copolymer, melt mass flow rate at 230 ° C., load 2.16 kg: 2.0 g / 10 min]
Thermoplastic elastomer:
-Hydrogenated SBR [manufactured by JSR Corporation, trade name: DYNARON1320P, 230 ° C., melt mass flow rate at a load of 2.16 kg: 3.5 g / 10 min]
R-TPO [polymerized polypropylene made of propylene and ethylene-propylene rubber, manufactured by Nippon Polypro Co., Ltd., trade name: Wellnex RFX4V, 230 ° C., melt mass flow rate at a load of 2.16 kg: 6.0 g / 10 min]
(Non-halogen flame retardant)
Flame retardant A; Phosphate compound [manufactured by ADEKA Corporation, trade name: ADK STAB FP2100J]
Flame retardant B: NOR-type hindered amine compound [BASF, trade name: FLAMESTABNOR116]
Flame retardant C: Phosphate ester [Daihachi Chemical Industry Co., Ltd., trade name: PX-200]
Flame retardant D: Magnesium hydroxide [Kyowa Chemical Industry Co., Ltd., trade name: Kisuma 5A]

[Examples 1 to 6 and Comparative Examples 1 to 4]
Each component is blended in the blending amounts shown in Table 1, and melt-kneaded at a screw diameter of 45 mm and a cylinder temperature of 200 ° C. using a twin-screw extruder (manufactured by Ikegai Co., Ltd., model name: PCM45) and discharged from a die The strand was cooled with a cooling bath and cut with a pelletizer to prepare a pelletized resin composition (pellet).
Next, the obtained pellets are used in an injection molding machine under the molding conditions of a cylinder temperature of 180 ° C. and a mold temperature of 30 to 50 ° C., a flame retardant test piece a, a test piece for specific gravity evaluation (large (127 mm × 12.7 mm, thickness: 1.6 mm), a test piece for flexibility evaluation was prepared, and for heat resistance molding, for the tensile characteristics and flame resistance under the molding condition of a heater temperature of 180 ° C. A test piece b was prepared and the performance test described above was performed. The results are shown in Table 1.

From all the examples in Table 1, the flame-retardant soft resin composition of the present invention is excellent in flame retardancy, flexibility, moldability, and mechanical properties (tensile properties), and a molded product having a low specific gravity is obtained. I understand that
On the other hand, in Comparative Example 1 in which the content of the flame retardant is larger than the specified range, the test piece is too hard to measure the surface hardness, and a low specific gravity and excellent moldability can be realized. Can not. Furthermore, in Comparative Example 2 where the content of the flame retardant is less than the specified range, it can be seen that excellent flame retardancy cannot be expressed. Moreover, from Comparative Examples 3 and 4 using magnesium hydroxide as a flame retardant, a large amount of magnesium hydroxide is required to develop flame retardancy, and it is impossible to achieve both flame retardancy and low specific gravity, Further, in Comparative Example 4 containing no polyolefin resin, the test piece was too hard to measure the surface hardness.

  The flame-retardant soft resin composition of the present invention is excellent in flame retardancy, flexibility, and mechanical properties (tensile properties), does not generate harmful gases such as halogen gas, and has a low specific gravity and good moldability. Because it is a resin composition that can be used, it must be flame retardant, flexible, mechanical properties (tensile properties), and lightweight, such as automotive parts, packaging materials, agricultural materials, home appliances, and packing materials for building materials. It can be used for the required molded products.

Claims (11)

  A resin composition containing 0.1 to 200 parts by mass of a non-halogen flame retardant excluding metal hydroxide with respect to 100 parts by mass of the resin, wherein the resin contains at least a polyolefin resin. object.   The flame-retardant soft resin composition according to claim 1, wherein the resin is a mixed resin containing a polyolefin-based resin and a thermoplastic elastomer.   The flame-retardant soft resin composition according to claim 1, wherein the resin contains a polyolefin-based resin and a thermoplastic elastomer at a blending ratio of mass ratio of 100: 0 to 1:99.   The flame-retardant soft resin composition according to any one of claims 1 to 3, wherein the polyolefin resin is one or more selected from a polypropylene resin and a polyethylene resin.   The flame-retardant soft resin composition according to any one of claims 2 to 4, wherein the thermoplastic elastomer is one or more selected from olefin-based elastomers and styrene-based elastomers.   The non-halogen flame retardant is one or more selected from phosphate compounds and derivatives thereof, red phosphorus, NOR type hindered amine compounds and derivatives thereof, phosphate esters and derivatives thereof, and sulfates and derivatives thereof. The flame-retardant soft resin composition according to any one of claims 1 to 5.   The flame-retardant soft resin composition according to any one of claims 1 to 6, wherein a molded product having a type A durometer hardness of 95 or less according to JIS K6253 is obtained.   The molded object obtained by injection-molding the flame-retardant soft resin composition in any one of Claims 1-7.   The molded object obtained by extrusion molding the flame-retardant soft resin composition in any one of Claims 1-7.   The laminated structure which has at least 1 layer which consists of a flame-retardant soft resin composition in any one of Claims 1-7.   The pellet obtained from the flame-retardant soft resin composition in any one of Claims 1-7.