JP4988398B2 - Flame retardant and flexible resin composition and molded body formed by molding the same - Google Patents

Description

  The present invention relates to a resin composition having a polylactic acid resin as a main component and excellent in flame retardancy and flexibility.

  Generally, resins such as polypropylene (PP), ABS (acrylonitrile-butadiene-styrene resin), polyamide (PA6, PA66), polyester (PET, PBT), and polycarbonate (PC) are used as raw materials for molding. . However, moldings produced from such resins are excellent in moldability and mechanical strength. However, when they are discarded, they increase the amount of dust and are hardly decomposed in the natural environment. Even if it remains in the ground semipermanently.

  On the other hand, in recent years, biodegradable polyester resins such as polylactic acid have attracted attention from the viewpoint of environmental conservation. Among the biodegradable resins, polylactic acid, polyethylene succinate, polybutylene succinate and the like are inexpensive and are highly useful because they can be mass-produced. Among them, polylactic acid has already been industrially produced from plants such as corn and sweet potato, and even if incinerated after use, considering the carbon dioxide absorbed during the growth of these plants, Since it is neutral, it is particularly regarded as a resin with a low impact on the global environment.

  However, when applying polylactic acid to a member that requires a certain degree of flexibility at the time of assembly, such as a nail fitting part of a housing of various electric products, the lack of flexibility is a problem as it is, In electrical products, of course, both flame retardancy and heat resistance have been demanded.

Several reports have already been made on imparting flexibility to polylactic acid.
For example, Patent Document 1 proposes a method of blending 16 to 33 wt% of an ester plasticizer with a polylactic acid resin. However, this method has a problem in terms of bleeding out. In addition, in imparting flexibility, it is desirable from the viewpoint of reducing the environmental load that the plant-derived nature of the polylactic acid resin is not impaired as much as possible. However, this plasticizer does not consider the environmental load. It was.

Patent Documents 2 and 3 propose a method of imparting flexibility by blending polybutylene succinate, which is a biodegradable environmentally friendly flexible resin, or an aliphatic-aromatic polyester resin into polylactic acid. ing. However, it has been difficult to improve the flame retardancy of a resin composition containing these resins even if a flame retardant is added.
JP 2006-265457 A JP-A-11-124430 JP 2006-070553 A

  The present invention is intended to solve the above-described problems, and an object of the present invention is to provide a flame retardant and flexible composition mainly composed of an environmentally friendly resin.

As a result of intensive studies to solve the above-mentioned problems, the present inventor uses polyamide 11 resin, which is an environmentally friendly resin, as a resin for imparting flexibility to a polylactic acid resin, and further blends a flame retardant. The inventors have found that the above-mentioned problems can be solved, and have reached the present invention.
That is, the gist of the present invention is as follows.
(1) A resin composition obtained by melt-kneading a mixture obtained by blending a polylactic acid resin and a polyamide 11 resin with a crosslinking aid, a peroxide, and a flame retardant, the polylactic acid resin and the polyamide 11 mass ratio (polylactic acid resin / polyamide 11 resin) is 97/3 to 70/30, the compounding amount of the crosslinking aid in the mixture is 0.01 to 5% by mass, and the compounding amount of the peroxide is 0.001 to 10 mass%, the amount of the flame retardant Ri 2-60% by mass, the flame retardant is a phosphorus flame retardant and / or aluminum hydroxide and / or magnesium hydroxide, phosphorus-based flame retardant and 0.2 to 3.0 wt% blending amount as elemental phosphorus, flame retardant and flexible amount of aluminum hydroxide and / or magnesium hydroxide, characterized in 20-60% by mass Rukoto Resin composition.
(2) The crosslinking aid is a compound having two or more (meth) acryl groups in the molecule, or one or more (meth) acryl groups and one or more glycidyl groups or vinyl groups. ( 1 ) The resin composition characterized by the above-mentioned.
(3) The resin composition as described in (1) or (2) , which contains 0.1 to 5 parts by mass of an organic crystal nucleating agent.
(4) A resin composition in which an organic crystal nucleating agent, a plasticizer, and a flame retardant are blended with a polylactic acid resin and a polyamide 11 resin, wherein the mass ratio of the polylactic acid resin and the polyamide 11 resin ( Polylactic acid resin / polyamide 11 resin) is 97/3 to 70/30, the compounding amount of the organic crystal nucleating agent in the resin composition is 0.1 to 5% by mass, and the compounding amount of the plasticizer is 1 to 10% by mass. , the amount of the flame retardant Ri 2-60% by mass, the flame retardant is a phosphorus flame retardant and / or aluminum hydroxide and / or magnesium hydroxide, the amount of phosphorus-based flame retardant is a phosphorus element 0.2 to 3.0 is the mass%, flame retardant and flexible resin composition amount of aluminum hydroxide and / or magnesium hydroxide, characterized in 20-60% by mass Rukoto.
(5) The resin composition as described in ( 4), wherein the plasticizer is an aliphatic ester derivative and / or an aliphatic polyether derivative.
(6) The organic crystal nucleating agent is N, N ′, N ″ -tricyclohexyltrimesic acid amide and / or N, N′-ethylenebis (12-hydroxystearic acid) amide and / or octane dicarboxylic acid It is acid dibenzoyl hydrazide, The resin composition in any one of ( 3 )-( 5 ) characterized by the above-mentioned.
(7) The resin composition as described in any one of (1) to ( 6 ), which contains 0.05 to 8% by mass of a hydrolysis inhibitor composed of a carbodiimide compound and / or an epoxy compound.
(6) A molded article obtained by molding the resin composition according to any one of (1) to ( 7 ).

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in a flame retardance, a softness | flexibility, and heat resistance can be provided. By using this resin composition for a casing of an electrical product, the range of use of polylactic acid resin, which is a low environmental load material, can be greatly expanded, and the industrial utility value is extremely high.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention includes a resin composition (A) obtained by melt-kneading a mixture formed by blending a polylactic acid resin, a polyamide 11 resin, a crosslinking aid, a peroxide, and a flame retardant, a polylactic acid resin, and a polyamide. 11 resin composition (B) comprising a resin, an organic crystal nucleating agent, and a plasticizer.

As the polylactic acid resin used in the resin composition of the present invention, poly (L-lactic acid), poly (D-lactic acid), and a mixture or copolymer thereof can be used in terms of heat resistance and moldability. However, from the viewpoint of biodegradability and molding processability, it is preferable that poly (L-lactic acid) is the main component.
Further, the melting point of the polylactic acid resin mainly composed of poly (L-lactic acid) varies depending on the optical purity, but in the present invention, the melting point is 160 ° C. in consideration of the mechanical properties and heat resistance of the molded product. The above is preferable. In a polylactic acid resin mainly composed of poly (L-lactic acid), in order to make the melting point 160 ° C. or higher, the ratio of the D-lactic acid component may be less than about 3 mol%.
The melt flow rate (for example, a value according to JIS standard K-7210 (test condition 4)) at 190 ° C. and a load of 21.2 N of the polylactic acid resin is usually 0.1 to 50 g / 10 minutes, preferably 0.2 to 20 g / 10 minutes, optimally 0.5 to 10 g / 10 minutes. When the melt flow rate exceeds 50 g / 10 min, the melt viscosity is too low, and the mechanical properties and heat resistance of the molded product may be inferior. On the other hand, when the melt flow rate is less than 0.1 g / 10 minutes, the load at the time of molding increases, and the operability may be lowered.
The polylactic acid resin is produced by a known melt polymerization method or by further using a solid phase polymerization method. Further, as a method for adjusting the melt flow rate of the biodegradable resin to a predetermined range, when the melt flow rate is too large, a small amount of chain extender, for example, a diisocyanate compound, a bisoxazoline compound, an epoxy compound, an acid anhydride And a method of increasing the molecular weight of the resin by using an object. Conversely, when the melt flow rate is too small, a method of mixing with a polyester resin or a low molecular weight compound having a large melt flow rate can be used.

  As the polyamide 11 resin used in the resin composition of the present invention, a resin having a melting point of 160 to 200 ° C. can be used. "Rilsan B" is listed.

  In the resin composition (A) of the present invention, the mass ratio of the polylactic acid resin and the polyamide 11 resin in the mixture (polylactic acid resin / polyamide 11 resin) needs to be 97/3 to 70/30, It is preferable that it is 95 / 5-70 / 30. In addition, the mass ratio of the polylactic acid resin and the polyamide 11 resin (polylactic acid resin / polyamide 11 resin) in the resin composition (B) must also be 97/3 to 70/30, and 95/5 to 70. / 30 is preferable. If the ratio of the polyamide 11 resin is less than 3% by mass, sufficient flexibility may not be obtained, and if it exceeds 30% by mass, the operability of extrusion during kneading may decrease.

The flame retardant used in the resin composition of the present invention is preferably at least one flame retardant selected from a phosphorus-based flame retardant, aluminum hydroxide, and magnesium hydroxide. The blending amount of the flame retardant in the mixture of the resin composition (A) and the blending amount of the flame retardant in the resin composition (B) are required to be 2 to 60% by mass.
Examples of the phosphorus-based flame retardant include phosphate ester-based and condensed phosphate ester-based ones. The compounding amount of the phosphorus-based flame retardant in the mixture of the resin composition (A) and the compounding amount of the phosphorus-based flame retardant in the resin composition (B) may be 0.2 to 3.0% by mass as the phosphorus element. preferable. If the blending amount is less than 0.2% by mass, sufficient flame retardancy may not be obtained, and if it exceeds 3.0% by mass, molding may be difficult, which is not preferable.
On the other hand, as aluminum hydroxide and magnesium hydroxide, common ones can be used, but those having an average particle size of 10 μm or less are preferred from the viewpoint of flame retardancy. It is preferable that the compounding quantity of the aluminum hydroxide and magnesium hydroxide in the mixture of a resin composition (A) and those compounding quantities in a resin composition (B) are 20-60 mass%. If the blending amount is less than 20% by mass, sufficient flame retardancy may not be obtained, and if it exceeds 60% by mass, kneading may be difficult, both of which are not preferable.

  The resin composition (A) of the present invention is obtained by melt-kneading a mixture in which the polylactic acid resin, the polyamide 11 resin, and the flame retardant are blended with a crosslinking aid and a peroxide. By blending a crosslinking aid and melt-kneading, the crystallization of the resin composition can be promoted and heat resistance can be improved. By blending a peroxide and melt-kneading, the crosslinking aid and poly Reaction with lactic acid resin can be promoted.

As the crosslinking aid used in the resin composition (A), two or more in the molecule because the reactivity with the polylactic acid resin is high, the monomer hardly remains, the toxicity is low, and the resin is less colored. Or a compound having one or more (meth) acryl groups and one or more glycidyl groups or vinyl groups.
Specific compounds include glycidyl methacrylate, glycidyl acrylate, glycerol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, allyloxy polyethylene glycol monoacrylate, allyloxy (poly) ethylene glycol monomethacrylate, (poly) ethylene glycol Dimethacrylate, (poly) ethylene glycol diacrylate, (poly) propylene glycol dimethacrylate, (poly) propylene glycol diacrylate, (poly) tetramethylene glycol dimethacrylate, or alkylenes with various lengths of these alkylene glycols And the like, butanediol methacrylate, butanediol acrylate, and the like.
In resin composition (A), the compounding quantity of the crosslinking adjuvant to a mixture needs to be 0.01-5 mass%, Preferably it is 0.05-1 mass%. If the blending amount is less than 0.01% by mass, the desired heat resistance cannot be obtained. If the blending amount exceeds 5% by mass, the operability during kneading decreases.

Specific examples of the peroxide used in the resin composition (A) include benzoyl peroxide, bis (butylperoxy) trimethylcyclohexane, bis (butylperoxy) cyclododecane, butylbis (butylperoxy) valerate, dicumyl Examples thereof include peroxide, butyl peroxybenzoate, dibutyl peroxide, bis (butylperoxy) diisopropylbenzene, dimethyldi (butylperoxy) hexane, dimethyldi (butylperoxy) hexyne, and butylperoxycumene.
In the resin composition (A), the amount of peroxide added to the mixture needs to be 0.001 to 10% by mass. If the blending amount is less than 0.001% by mass, the desired heat resistance cannot be obtained, and if it exceeds 10% by mass, the operability during kneading may be lowered. In addition, since a peroxide decomposes | disassembles and is consumed in the case of melt mixing of a mixture, it may not remain | survive in the resin composition (A) obtained.

  The resin composition (A) of the present invention can be produced by melt-kneading a mixture comprising a polylactic acid resin, a polyamide 11 resin, a crosslinking aid, a peroxide, and a flame retardant. The melt kneading can be performed using a single screw or twin screw extruder. In order to improve the kneading state, it is preferable to use a twin screw extruder. The kneading temperature is preferably in the range of (melting point of polylactic acid resin + 5 ° C.) to (melting point of polylactic acid resin + 100 ° C.), and the kneading time is preferably from 20 seconds to 30 minutes. When the temperature is lower than this range or for a short time, kneading or reaction becomes insufficient. On the other hand, when the temperature is high or for a long time, the resin may be decomposed or colored.

  In contrast to the resin composition (A), the resin composition (B) of the present invention is obtained by adding an organic crystal nucleating agent and a plasticizer to a polylactic acid resin, a polyamide 11 resin, and a flame retardant. By adding an organic crystal nucleating agent, crystallization of the resin composition can be promoted and heat resistance can be improved, and by adding a plasticizer, dispersion of the organic crystal nucleating agent into the polylactic acid resin can be promoted. Can do.

Examples of the organic crystal nucleating agent used in the resin composition (B) of the present invention include one or more organic crystal nucleating agents represented by the general formulas (1) to (3). Specific examples of the compound include N, N ′, N ″ -tricyclohexyltrimesic acid amide, N, N′-ethylenebis (12-hydroxystearic acid) amide, octanedicarboxylic acid dibenzoyl hydrazide, and the like. .
R ^1- (CONH-R ² ) _a (1)
[Wherein, R ¹ represents a saturated or unsaturated aliphatic chain having 2 to 30 carbon atoms, a saturated or unsaturated aliphatic ring, or an aromatic ring. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, a phenyl group, a naphthyl group, an anthryl group, or the formula (a) The group represented by any one of (d) is represented. a represents an integer of 2 to 6. ]
[Wherein R ³ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a phenyl group, or a halogen atom. Represents an atom. l represents an integer of 1 to 5. ]
[Wherein, R ⁴ represents a linear or branched alkylene group having 1 to ⁴ carbon atoms. R ⁵ has the same meaning as R ³ described above. m represents an integer of 0 to 5. ]
[Wherein, R ⁶ has the same meaning as R ³ described above. n represents an integer of 1 to 5. ]
[Wherein, R ⁷ has the same meaning as R ⁴ above, and R ⁸ has the same meaning as R ³ above. o represents an integer of 0-6. ]
_{^{R 9 - (NHCO-R 10}} ) f (2)
[Wherein R ⁹ represents a saturated or unsaturated fatty chain having 2 to 30 carbon atoms, an unsaturated alicyclic ring, or an aromatic ring. R ¹⁰ has the same meaning as R ² described above. f represents an integer of 2-6. ]
_{^{R 11 - (CONHNHCO-R 12}} ) h (3)
[Wherein R ¹¹ represents a saturated or unsaturated fatty chain having 2 to 30 carbon atoms, an unsaturated alicyclic ring, or an aromatic ring. R ¹² has the same meaning as R ² described above. h represents an integer of 2 to 6. ]

The compounding amount of the organic crystal nucleating agent in the resin composition (B) is required to be 0.1 to 5% by mass, and preferably 0.5 to 3% by mass. If the blending amount is less than 0.1% by mass, the desired heat resistance cannot be obtained, and if it exceeds 5% by mass, the operability during kneading is lowered.
In addition, the said organic crystal nucleating agent may be mix | blended with a resin composition (A), and the crystallization of a resin composition may be further accelerated | stimulated, It is preferable that the compounding quantity is 0.1-5 mass%. .

The plasticizer used in the resin composition (B) of the present invention is preferably at least one plasticizer selected from aliphatic ester derivatives and aliphatic polyether derivatives. Specific examples of the compound include glycerin diacetomonocaprate and glycerin diacetomonolaurate.
The compounding quantity of the plasticizer in a resin composition (B) needs to be 1-10 mass%. When the content is less than 1% by mass, the intended effect cannot be obtained, and when the content exceeds 10% by mass, the operability during kneading is lowered.

  The resin composition (B) of the present invention contains a polylactic acid resin, a polyamide 11 resin, an organic crystal nucleating agent, a plasticizer, and a flame retardant. The means for mixing these is not particularly limited, and examples thereof include a melt kneading method using a single screw or twin screw extruder. In order to improve the kneading state, it is preferable to use a twin screw extruder. The kneading temperature is preferably in the range of (melting point of polylactic acid resin + 5 ° C.) to (melting point of polylactic acid resin + 100 ° C.), and the kneading time is preferably from 20 seconds to 30 minutes. When the temperature is lower than this range or for a short time, kneading or reaction becomes insufficient. On the other hand, when the temperature is high or for a long time, the resin may be decomposed or colored.

The resin composition of the present invention may contain a hydrolysis inhibitor. By containing a hydrolysis inhibitor, the durability of the resin composition can be improved, and its flame retardancy and heat resistance can be stably maintained for a long period of time.
In the present invention, the hydrolysis inhibitor is one or more compounds selected from carbodiimide compounds and epoxy compounds. Various substances can be used as the specific substance, and it is particularly preferable to use a carbodiimide compound containing an isocyanate group. The carbodiimide compound containing an isocyanate group is not particularly limited as long as it has a structure in which an isocyanate group is introduced into a compound having one or more carbodiimide groups in the molecule, and the carbodiimide skeleton includes N, N′-di- -O-triylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N-triyl-N'-phenylcarbodiimide N, N′-di-p-nitrophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-triylcarbodiimide, p-phenylene-bis-di-o-triylcarbodiimide, , 4'-dicyclohexylmethane carbodiimide, tetramethylxylylene carbodiimide, N, N-dimethyl-phenyl carbodiimide, N, etc. N'- di-2,6-diisopropylphenyl carbodiimide and the like.
The content of the hydrolysis inhibitor in the resin composition of the present invention is preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. If the content is less than 0.05% by mass, the intended durability may not be obtained, and if it exceeds 8% by mass, the color tone may be greatly impaired.

A pigment, a heat stabilizer, an antioxidant, an inorganic filler, a vegetable fiber, a weathering agent, a lubricant, a release agent, an antistatic agent, and the like are added to the resin composition of the present invention as long as the characteristics are not significantly impaired. be able to.
Examples of heat stabilizers and antioxidants include hindered phenols, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.
Examples of the inorganic filler include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesia, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black Zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, carbon fiber and the like are exemplified.
Examples of plant fibers include kenaf fibers.
In addition, the method of mixing these with the resin composition of this invention is not specifically limited.

  The resin composition of the present invention can be formed into various molded products by molding methods such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing. In particular, it is preferable to adopt an injection molding method, and in addition to a general injection molding method, gas injection molding, injection press molding, and the like can be employed. As an example of injection molding conditions suitable for the resin composition of the present invention, the cylinder temperature is equal to or higher than the melting point or flow start temperature of the resin composition, preferably 170 to 250 ° C, optimally in the range of 170 to 230 ° C, Further, it is appropriate that the mold temperature is not higher than (melting point-20 ° C.) of the resin composition. If the molding temperature is too low, the operability becomes unstable, such as short-circuiting in the molded product, and overload tends to occur. Conversely, if the molding temperature is too high, the resin composition will decompose and the resulting molded product Problems such as reduction in strength and coloration are likely to occur, and both may be undesirable.

  The heat resistance of the resin composition of the present invention can be further improved by promoting crystallization during molding. As a method for this purpose, for example, there is a method of promoting crystallization in a mold at the time of injection molding. A method in which the molded body is held for a certain period of time in a mold held in a mold and then taken out from the mold is preferable. Moreover, even if it is the molded object taken out from the metal mold | die without taking such a method, crystallization is accelerated | stimulated again by heat-processing above the glass transition temperature and below (melting | fusing point-20 degreeC). it can.

  Specific examples of the molded body using the resin composition of the present invention include personal computer casing parts and casings, mobile phone casing parts and casings, other resin parts for electrical appliances such as OA equipment casing parts, bumpers, Examples include resin panels for automobiles such as instrument panels, console boxes, garnishes, door trims, ceilings, floors, and panels around the engine. Moreover, it can also be set as a film, a sheet | seat, a hollow molded product, etc.

Hereinafter, the present invention will be described more specifically with reference to examples. The measuring method used for evaluation of the resin composition of an Example and a comparative example is as follows.
(1) Deflection temperature under load:
Based on ASTM D648, the heat distortion temperature was measured at a load of 0.45 MPa. The heat distortion temperature is preferably 80 ° C. or higher.
(2) Flame retardancy:
Measured according to UL94. A test piece having a thickness of 1.5 mm was used. The flame retardancy is preferably V-0.
(3) Flexural modulus, flexural strength retention:
Measured according to ASTM D790. The flexural modulus is preferably 3.4 GPa or less. The bending strength was measured after the bending test piece was exposed to a high temperature and high humidity environment of 60 ° C. and 95% RH for 20 days. Even after leaving under high temperature and high humidity, it is preferable to maintain a bending strength of 60% or more before leaving.

Moreover, the various raw materials used for the Example and the comparative example are as follows.
(1) Polylactic acid resin:
Cargill Dow “6201D”
(2) Crosslinking aid:
Ethylene glycol dimethacrylate ("Blemmer PDE-50" manufactured by NOF Corporation)
(3) Flexible resin:
Polyamide 11 resin ("Rilsan B" manufactured by Arkema, Inc., hereinafter referred to as PA11)
Polybutylene succinate resin ("GSPla" manufactured by Mitsubishi Chemical Corporation (hereinafter referred to as PBS)
Polybutylene adipate terephthalate resin ("Eco-Flex" manufactured by BASF, hereinafter referred to as PBAT)
(4) Hydrolysis inhibitor:
Isocyanate-modified carbodiimide (“LA-1” manufactured by Nisshinbo Co., Ltd., isocyanate group content 1 to 3%, hereinafter referred to as LA)
Epoxy compound ("Denacol EX-810" manufactured by Nagase ChemteX Corp .; hereinafter referred to as EX)
(5) Peroxide:
Di-t-butyl peroxide (“Perbutyl D” manufactured by NOF Corporation)
(6) Organic crystal nucleating agent:
N, N ′, N ″ -tricyclohexyltrimesic acid amide (“TF-1” manufactured by Shin Nippon Chemical Co., Ltd., hereinafter referred to as TF-1)
N, N′-ethylenebis-12-hydroxystearic acid amide (“T-530SF” manufactured by Ito Oil Co., Ltd., hereinafter referred to as “530SF”)
Octanedicarboxylic acid dibenzoyl hydrazide ("T-1287N" manufactured by Adeka Corporation; hereinafter referred to as 1287N)
(7) Plasticizer:
Glycerin diacetomonocaprate ("PL-019" manufactured by Riken Vitamin)
(8) Phosphorus flame retardant:
Condensed phosphate ester (Daihachi Chemical "PX200". Phosphorus element content 9.0%)
(9) Aluminum hydroxide:
“Hijilite H-32” manufactured by Showa Denko (average particle size: 3.5 μm)
(10) Magnesium hydroxide:
“Kisuma 5” manufactured by Kyowa Chemical Industry Co., Ltd. (average particle size 0.8μm)

Example 1
Polylactic acid resin (72.4 parts by mass), PA11 (8 parts by mass), phosphorus-based flame retardant (17 parts by mass), organic crystal nucleating agent TF-1 (0.8 parts by mass), and hydrolysis inhibition After dry blending with the agent LA (1.5 parts by mass), these are supplied from the root supply port of a twin screw extruder (TEM37BS type manufactured by Toshiba Machine Co., Ltd.), barrel temperature 180 ° C., screw rotation speed 280 rpm, discharge Extrusion was carried out under the condition of 15 kg / h while venting, and a crosslinking aid (0.10 parts by mass) and 0.2 parts by mass of peroxide were supplied into the cylinder. The resin discharged from the tip of the extruder was cut into pellets to obtain pellets of the resin composition.
The obtained pellets were vacuum-dried at 70 ° C. for 24 hours, and then a test piece for measuring general physical properties (ASTM) while adjusting the mold surface temperature to 105 ° C. using an IS-80G injection molding machine manufactured by Toshiba Machine Co., Ltd. Mold) and prepared for various measurements. At this time, the filling / holding time was fixed at 30 seconds, and the cooling time during which the test piece was sufficiently cured and could be taken out was determined.

Examples 2-14, Comparative Examples 1-12
Resin composition pellets were obtained in the same manner as in Example 1 except that the amount and type of each component were changed so as to obtain the blending amounts shown in Table 1, and various physical properties were measured by injection molding.

  Table 1 summarizes the evaluation results of Examples 1 to 14 and Comparative Examples 1 to 12.

As can be seen from Table 1, in Examples 1 to 14, it was found that a resin composition excellent in flame retardancy, flexibility, heat resistance, and moldability was obtained. In Examples 1 to 8 and 12 to 14, the blending amount of the hydrolysis inhibitor was appropriate, so that it was more suitable in terms of durability or color tone than Examples 9 to 11. Results were obtained. Moreover, in Examples 1-11, since the compounding quantity of the organic crystal nucleating agent was appropriate, more favorable results were obtained in moldability and operability during kneading as compared with Examples 12-14. It was.
On the other hand, in the comparative example 1, since PA11 was not mix | blended, it became a result inferior to a softness | flexibility. In Comparative Example 2, since the amount of the phosphorus-based flame retardant was small, the result was inferior in flame retardancy. In Comparative Example 3, molding was difficult because the amount of the phosphorus-based flame retardant was large. In Comparative Example 4, since the amount of aluminum hydroxide was small, the result was inferior in flame retardancy. In Comparative Example 5, kneading was difficult because of the large amount of aluminum hydroxide. Moreover, in Comparative Example 6, since the amount of the crosslinking aid was small, the heat resistance was inferior. In Comparative Example 7, kneading was difficult because the amount of the crosslinking aid was large. In Comparative Example 8, molding was difficult because the amount of peroxide was small. In Comparative Examples 9 and 10, since PBS and PBAT were used as the flexible resin instead of PA11, the results were poor in flame retardancy and moldability. Although the blending amount of the flame retardant was increased in Comparative Examples 11 and 12, the flame retardancy was not improved in the resin composition using PBS or PBAT as the flexible resin.

Example 15
Polylactic acid (68 parts by mass), PA11 (8 parts by mass), phosphorus-based flame retardant (17 parts by mass), organic crystal nucleating agent 530SF (1.5 parts by mass), and hydrolysis inhibitor LA (1. 5 parts by mass) are dry blended and then supplied from the root supply port of a twin screw extruder (TEM37BS manufactured by Toshiba Machine Co., Ltd.) under conditions of barrel temperature 180 ° C., screw rotation speed 280 rpm, discharge 15 kg / h Then, extrusion was performed while venting was applied, and further, a plasticizer (4 parts by mass) was supplied into the cylinder. The resin discharged from the tip of the extruder was cut into pellets to obtain pellets of the resin composition.
The obtained pellets were vacuum-dried at 70 ° C. for 24 hours, and then a test piece for measuring general physical properties (ASTM) while adjusting the mold surface temperature to 105 ° C. using an IS-80G injection molding machine manufactured by Toshiba Machine Co., Ltd. Mold) and prepared for various measurements. At this time, the filling / holding time was fixed at 30 seconds, and the cooling time during which the test piece was sufficiently cured and could be taken out was determined.

Examples 16 to 25, Comparative Examples 13 to 23
Resin composition pellets were obtained in the same manner as in Example 15 except that the amount and type of each component were changed so that the content shown in Table 2 was obtained, and this was injection molded to measure various physical properties.

  Table 2 summarizes the evaluation results of Examples 15 to 25 and Comparative Examples 13 to 23.

As apparent from Table 2, in Examples 15 to 25, it was found that resin compositions having excellent flame retardancy, flexibility, heat resistance, and moldability were obtained. In Examples 15 to 22, since the amount of the hydrolysis inhibitor was appropriate, more favorable results were obtained in terms of durability and color tone as compared with Examples 23 to 25.
On the other hand, in Comparative Example 13, since PA11 was not blended, the results were inferior in flexibility. In Comparative Example 14, since the blending amount of the phosphorus-based flame retardant was small, the result was inferior in flame retardancy. In Comparative Example 15, molding was difficult because the amount of the phosphorus-based flame retardant was large. In Comparative Example 16, since the amount of aluminum hydroxide was small, the result was inferior in flame retardancy. In Comparative Example 17, kneading was difficult because of the large amount of aluminum hydroxide. In Comparative Example 18, since the amount of the organic crystal nucleating agent was small, the heat resistance was poor. In Comparative Example 19, kneading was difficult because the amount of the organic crystal nucleating agent was large. In Comparative Example 20, since the amount of the plasticizer was small, the heat resistance was poor. In Comparative Example 21, kneading was difficult because of the large amount of plasticizer. In Comparative Examples 22 and 23, PBS and PBAT were used as the flexible resin instead of PA11, resulting in poor flame retardancy and moldability.

Claims (8)

A resin composition obtained by melt-kneading a mixture formed by blending a polylactic acid resin and a polyamide 11 resin with a crosslinking aid, a peroxide, and a flame retardant, wherein the polylactic acid resin and the polyamide 11 resin Mass ratio (polylactic acid resin / polyamide 11 resin) is 97/3 to 70/30, the compounding amount of the crosslinking aid in the mixture is 0.01 to 5% by mass, and the compounding amount of the peroxide is 0.001. 10 wt%, Ri amount is 2 to 60% by mass of the flame retardant, a flame retardant, a phosphorus-based flame retardant and / or aluminum hydroxide and / or magnesium hydroxide, the amount of phosphorus-based flame retardant There is a 0.2 to 3.0 wt% as phosphorus, a flame retardant amount of aluminum hydroxide and / or magnesium hydroxide, characterized in 20-60% by mass Rukoto and flexible resin composition . The crosslinking aid is a compound having two or more (meth) acryl groups in the molecule, or one or more (meth) acryl groups and one or more glycidyl groups or vinyl groups. The resin composition according to claim 1 . The resin composition according to claim 1 or 2 , comprising 0.1 to 5 parts by mass of an organic crystal nucleating agent. A resin composition comprising a polylactic acid resin, a polyamide 11 resin, an organic crystal nucleating agent, a plasticizer, and a flame retardant, wherein the mass ratio of the polylactic acid resin to the polyamide 11 resin (polylactic acid resin) / Polyamide 11 resin) is 97/3 to 70/30, the compounding amount of the organic crystal nucleating agent in the resin composition is 0.1 to 5% by mass, the compounding amount of the plasticizer is 1 to 10% by mass, and the flame retardant amount is 2 to 60% by mass of is, the flame retardant is a phosphorus flame retardant and / or aluminum hydroxide and / or magnesium hydroxide, 0.2 amount of phosphorus-based flame retardant is a phosphorus element 3.0 is the mass%, flame retardant and flexible resin composition amount of aluminum hydroxide and / or magnesium hydroxide, characterized in 20-60% by mass Rukoto. The resin composition according to claim 4, wherein the plasticizer is an aliphatic ester derivative and / or an aliphatic polyether derivative. The organic crystal nucleating agent is N, N ′, N ″ -tricyclohexyltrimesic acid amide and / or N, N′-ethylenebis (12-hydroxystearic acid) amide and / or dibenzoyl octanedicarboxylate The resin composition according to claim 3 , which is hydrazide. The resin composition according to any one of claims 1 to 6 , comprising 0.05 to 8% by mass of a hydrolysis inhibitor composed of a carbodiimide compound and / or an epoxy compound. Molded article obtained by molding the resin composition according to any one of claims 1-7.