JP5300669B2 - Flame retardant resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having satisfactory flame retardnacy, flexural properties (flexibility), impact resistance, heat resistance, wet heat resistance and moldability, and to provide a method for producing the resin composition. <P>SOLUTION: The resin composition includes 25 to 85 pts.mass polylactic acid resin, 10 to 40 pts.mass flame retardant, 5 to 55 pts.mass glass fiber, 0.1 to 10 pts.mass hydrolysis inhibitor, 0.03 to 5 pts.mass barium organic sulfonate, and 1 to 15 pts.mass glycidyl methacrylate modified core-shell type impact resistant agent in 100 pts.mass total composition. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a flame retardant resin composition containing a polylactic acid resin.

  Generally, as raw materials for molding various molded products, polypropylene (PP), acrylonitrile-butadiene-styrene resin (ABS resin), polyamide resins such as nylon 6 and nylon 66, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT) ) And other resins such as polycarbonate (PC). Molded bodies manufactured from such resins are excellent in moldability and mechanical strength, but when discarded, they increase the amount of dust and are hardly decomposed in the natural environment. There is a problem that it remains in the ground semipermanently.

  On the other hand, in recent years, biodegradable polyester resins such as polylactic acid resins have attracted attention from the viewpoint of environmental conservation. Among biodegradable polyester resins, polylactic acid, polyethylene succinate, polybutylene succinate, and the like have the advantages of low cost and high usefulness because they can be mass-produced. Among them, polylactic acid resin can already be 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, it is neutral as a carbon balance. In particular, it is a resin that has a low impact on the global environment.

  However, when the polylactic acid resin is used alone for a housing of an electric product or the like, there is a safety problem because the flame retardancy of the polylactic acid resin is insufficient. Furthermore, in the case of a housing such as an electric product, in many cases, heat resistance that can withstand a high temperature environment exceeding at least 100 ° C. is required. Accordingly, there is a demand for a polylactic acid resin having both flame retardancy and heat resistance. Needless to say, it is necessary to have durability and impact resistance as usual.

  Of the above properties, the flame retardancy is naturally improved by blending the flame retardant in a high ratio. Further, it is easily considered from the conventionally known knowledge that the heat resistance, particularly the deflection temperature under load under a large load (for example, 1.8 MPa) is improved by blending the reinforcing filler at a high ratio. However, it is not preferable to add a flame retardant or reinforcing filler in a high ratio because the ratio of polylactic acid in the entire resin composition is reduced and the usefulness to the environment is reduced. Therefore, it is required that polylactic acid is blended in the resin composition at a high ratio (for example, more than half of the entire resin composition) and the physical properties such as durability and impact resistance are satisfied.

  Addition of organic filler and flame retardant to polylactic acid resin and injection molding at a mold temperature of 90 ° C., flame retardancy from V-2 to V-0 and heat resistance above a certain level in UL94 test It is known that a molded body having the above is obtained (for example, see Patent Document 1). However, in this case, the heat resistance is improved by adding a high ratio of naturally-occurring organic fillers such as used paper powder, so heat discoloration cannot be avoided during melting during kneading or molding. There is a problem that it is difficult to adjust. Furthermore, with respect to the after-flame time after flame contact after satisfying the flame retardancy of V-0, there is a possibility that ignition may occur if the after-flame time is long when used as a casing of an electric product or the like. There are safety issues. Furthermore, the heat resistance imparted by the flame retardant composition described in Patent Document 1 (for example, aromatic condensed phosphate ester, melamine cyanurate, etc.) is at a low level. For example, the deflection temperature under load is low. Even in the case of a small load (0.45 MPa), it is about 110 ° C. In addition, the Izod impact value is as low as less than 25 J / m, and sufficient impact resistance is not obtained.

  In addition, it is known that a flame retardant property and a certain amount of heat resistance are imparted to a polylactic acid resin by adding a surface-treated metal hydroxide (see, for example, Patent Document 2). However, in this case, the flame retardancy obtained is at the V-2 level, which is still insufficient when used for a casing of the electric product or the like.

  In addition, it is known to use a phosphinic acid-based compound (for example, a free acid such as dimethylphosphinic acid) to make a mesh sheet containing a polylactic acid resin flame-retardant (for example, see Patent Document 3). . However, even in this case, a high flame retardant level has not yet been obtained.

  In addition, a flame-retardant polylactic acid resin composition using an organic carboxylic acid metal salt as a metal salt-based crystal nucleating agent is known (for example, see Patent Document 4). However, even in this case, excellent flame retardancy and formability that can withstand use in a casing of the electric product or the like have not been obtained.

  In addition, a flame retardant polylactic acid resin composition using a fluororesin-based anti-drip agent such as polytetrafluoroethylene is known (see, for example, Patent Document 5). However, in this case, a flame retardant level of V-0 (thickness 1.6 mm) is required unless a large amount of flame retardant is added and the ratio of the polylactic acid resin is suppressed to less than 50% by mass with respect to the entire resin composition Cannot be obtained, and the level is insufficient to make use of the environmental merits of polylactic acid.

  Further, it is known to impart impact resistance to a polylactic acid resin composition using a core-shell type impact resistance agent, and certain impact resistance is obtained (see, for example, Patent Document 6). However, in this case, the level for examining durability is low (60 ° C. × 95% RH × 200 hours), and the strength retention is low. In this case, sufficient heat resistance is not obtained.

  In addition, it is known to use an alkaline earth metal compound such as a barium compound, a glycidyl ester compound and a core-shell type impact agent in order to impart flame retardancy and mechanical properties to the polylactic acid resin (for example, (See Patent Document 7). However, in this case, excellent flame retardancy and moldability are not obtained.

  In addition, a flame-retardant polylactic acid-based composition to which a sulfonic acid compound such as an organic sulfonate is added is known (see, for example, Patent Document 8). However, in this case as well, the flame retardancy imparted is at the V-2 level and cannot be said to be sufficient.

  In addition, Mitsubishi Rayon Co., Ltd. shows in the form of various sales promotion materials that it is possible to obtain an impact resistance improvement effect and a heat resistance improvement effect on polylactic acid resin by using a glycidyl methacrylate modified core-shell type impact agent. However, no mention is made of flame retardancy and durability, and it is not shown as a composition.

Japanese Patent Laid-Open No. 2005-23260 JP-A-2005-139441 JP 2005-105472 A JP 2006-193561 A Table 2005/061626 JP 2006-016447 A JP 2006-016446 A JP 2008-303290 A

  The present invention solves the above-mentioned problems, and even when the plant-derived ratio is high, the flame retardancy, bending physical properties (flexibility), impact resistance, heat resistance, moist heat resistance and moldability are good. It aims at providing a flame retardant resin composition.

As a result of intensive research to solve the above problems, the present inventors have made polylactic acid resin, organic phosphinic acid metal salt flame retardant, glass fiber, hydrolysis inhibitor, organic sulfonic acid barium salt and glycidyl methacrylate modified. The present inventors have found that resin compositions containing core-shell impact agents at a specific ratio are resin compositions in which the above-mentioned problems have been solved, and have reached the present invention.

That is, the gist of the present invention is as follows.
(1) Of the total 100 parts by mass, the polylactic acid resin is 25 to 85 parts by mass, the organic phosphinic acid metal salt flame retardant is 10 to 40 parts by mass, the glass fiber is 5 to 55 parts by mass, and the hydrolysis inhibitor is 0. A flame-retardant resin composition comprising 1 to 10 parts by mass, 0.03 to 5 parts by mass of an organic sulfonic acid barium salt, and 1 to 15 parts by mass of a glycidyl methacrylate-modified core-shell impact agent .
(2 ) The flame retardant resin composition according to (1 ), comprising 0.1 to 1 part by mass of a fluororesin-based anti-drip agent.
( 3 ) The flame-retardant resin composition according to (1) or (2) , which contains 50 parts by mass or more of a polylactic acid resin.
( 4 ) The flame retardant according to any one of (1) to ( 3 ), characterized by being melt-kneaded together with 0.01 to 20 parts by mass of (meth) acrylic acid ester compound and 0.1 to 20 parts by mass of peroxide. Resin composition.
( 5 ) The flame retardant resin composition according to any one of (1) to ( 4 ), wherein the ratio of the D-form component in the polylactic acid resin is 0.6 mol% or less.
( 6 ) It is a manufacturing method of a flame retardant resin composition, Comprising: Polylactic acid resin 25-85 mass parts among 10 mass parts in total, 10-40 mass parts of organic phosphinic acid metal salt flame retardants, glass fiber 5 to 55 parts by mass, 0.1 to 10 parts by mass of a hydrolysis inhibitor, 0.03 to 5 parts by mass of an organic sulfonic acid barium salt, and 1 to 15 parts by mass of a glycidyl methacrylate-modified core shell impact modifier A method for producing a flame retardant resin composition.

  According to the present invention, even if the plant-derived ratio is high and the plant-derived ratio is high, the flame retardancy is excellent in flame retardancy, moldability, bending physical properties (flexibility), impact resistance, heat resistance, and moist heat resistance. A resin composition can be provided. By using this resin composition for parts of electrical products, 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 flame-retardant resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) includes a polylactic acid resin, an organic phosphinic acid metal salt flame retardant, glass fiber, a hydrolysis inhibitor, and an organic sulfonic acid. It contains a barium salt and a glycidyl methacrylate-modified core-shell impact agent.

Hereinafter, various raw materials used in the present invention will be described.
The polylactic acid resin is a resin mainly composed of polylactic acid. As polylactic acid, poly (L-lactic acid), poly (D-lactic acid), and a mixture thereof, or a copolymer thereof can be used. From the viewpoint of biodegradability and molding processability, It is preferable to mainly use poly (L-lactic acid).

  The melting point of the polylactic acid resin mainly composed of poly (L-lactic acid) varies depending on the optical purity. However, in the present invention, the melting point is set to 160 ° C. or more in consideration of the mechanical properties and heat resistance of the molded body. It is preferable. The upper limit of the melting point of polylactic acid resin that is generally used is about 190 ° C. In the polylactic acid resin mainly composed of poly (L-lactic acid), in order to make the melting point 160 ° C. or higher, the poly (D-lactic acid) may be less than about 3 mol% with respect to the whole polylactic acid. .

  Furthermore, from the viewpoint of moldability and heat resistance of the resin composition, in the polylactic acid resin mainly composed of poly (L-lactic acid), the proportion of poly (D-lactic acid) is particularly 0.6 mol% or less. preferable.

  Content of polylactic acid resin is 25-85 mass parts among 100 mass parts of resin compositions, Preferably it is 30-85 mass parts, Most preferably, it is 35-75 mass parts. When the content is less than 25 parts by mass, the usefulness to the environment is insufficient. On the other hand, when the content exceeds 85 parts by mass, other essential components cannot be contained in a predetermined amount, and the object of the present invention. The effect cannot be obtained. Furthermore, it is preferable that the content of the polylactic acid resin is 50 parts by mass or more from the viewpoint of usefulness to the environment, particularly the effect of fixing and storing carbon dioxide in the atmosphere.

The polylactic acid resin is produced by polymerizing polylactic acid by a known melt polymerization method or by adding a solid phase polymerization method to the melt polymerization method.
The melt flow rate (MFR) 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, and more preferably 0.5 to 10 g / 10 min. When the melt flow rate exceeds 50 g / 10 min, the melt viscosity is too low and the molded article may have poor mechanical properties and heat resistance. When the melt flow rate is less than 0.1 g / 10 min, the load during the molding process becomes too high, and the operability may be lowered. In the present invention, MFR is a value measured in accordance with JIS K-7210 (test condition D).

  As a method for controlling the melt flow rate of the polylactic acid resin within a predetermined range, when the melt flow rate is too large, a method of increasing the molecular weight of the resin by using a small amount of chain extender can be mentioned. Although it does not specifically limit as a chain extension agent, For example, a diisocyanate compound, a bisoxazoline compound, an epoxy compound, an acid anhydride etc. can be used. On the contrary, when the melt flow rate is too small, a method of adding a polylactic acid resin having a higher melt flow rate or a low molecular weight compound can be mentioned.

  As the polylactic acid resin, a commercially available product can be suitably used, and examples thereof include trade names “S-09”, “S-12”, and “S-17” manufactured by Toyota.

The flame retardant is contained for the purpose of suppressing the flammability of the resin composition and imparting a certain flame retardancy .

Although the halogen-based flame retardant is excellent in the flame retardant effect, it is unsuitable based on the gist of the present invention because it has a large environmental load .
In the present invention, from the viewpoint of a balance to the load on the flame retardancy and environment In view of excellent flame retardancy improving effect, and heat resistance, required to be a flame retardant of an organic phosphinic acid metal salt-based There is .

  Any known organic phosphinic acid metal salt flame retardant can be used. By containing an organic phosphinic acid metal salt flame retardant, even when a large amount of highly flammable polylactic acid resin is contained, combustion can be effectively suppressed. Furthermore, a good effect can be expected in heat resistance. As the organic phosphinic acid metal salt flame retardant, a commercially available product can also be suitably used, and examples thereof include a product name “Exorit OP series” manufactured by Clariant.

The above organic phosphinic acid metal salt flame retardants are used alone or in combination of two or more.
The content of the organic phosphinic acid metal salt flame retardant is 10 to 40 parts by mass, preferably 15 to 35 parts by mass, and particularly preferably 18 to 35 parts by mass, out of 100 parts by mass of the resin composition. When the content is less than 10 parts by mass, sufficient flame retardancy cannot be obtained. On the other hand, when the content exceeds 40 parts by mass, physical properties such as impact resistance and fracture strain of the resulting resin composition are reduced. There is a problem, and further, there is a problem that the operability at the time of kneading is lowered.

An organic sulfonic acid barium salt is added to the resin composition of the present invention for the purpose of promoting crystallization and obtaining heat resistance and good moldability. By containing an organic sulfonic acid barium salt, crystallization can be effectively promoted without inhibiting the flame retardant effect of the organic phosphinic acid metal salt flame retardant. The organic sulfonic acid barium salt has a small adverse effect on flame retardancy compared with other crystal nucleating agents, and is excellent in the crystallization promoting effect. The reason why such an effect is obtained is not clear, but it is presumed that a special effect on the molecular structure is probably expressed by a combination of sulfur element and barium element.

  Content of organic sulfonic acid barium salt is 0.03-5 mass parts among 100 mass parts of resin compositions, Preferably it is 0.05-5 mass parts, Most preferably, it is 0.1-4 mass parts. It is. When the said content is less than 0.03 mass part, crystallization of the resin composition obtained is accelerated | stimulated and sufficient heat resistance and a moldability cannot be provided. On the other hand, when it exceeds 5 parts by mass, there is a problem that physical properties such as impact resistance and breaking strain of the obtained resin composition are lowered, and further, there is a problem that operability during kneading is lowered.

  Commercially available products can be suitably used as the organic sulfonic acid barium salt, and examples thereof include trade name “TLA114” manufactured by Takemoto Yushi Co., Ltd.

  The resin composition of the present invention contains glass fibers for the purpose of increasing the fastness of the resin composition and improving the heat resistance. Glass fibers having any shape can be used.

  Content of glass fiber is 5-55 mass parts among 100 mass parts of resin compositions, Preferably it is 8-52 mass parts, Most preferably, it is 10-50 mass parts. If it is less than 5 parts by mass, it is impossible to obtain the necessary combustion particle dripping suppressing effect (that is, the drop preventing effect) and the load deflection suppressing effect. On the other hand, when it exceeds 55 parts by mass, kneading becomes difficult and the content of other necessary components is greatly restricted, and the effects of the present invention cannot be satisfied.

As glass fiber, normal glass fiber can be used.
Owens Corning, trade name “FT592” or the like is preferably used. In addition, the glass fiber may be subjected to a well-known and conventional surface treatment for enhancing the adhesion with other resins.

  The resin composition of the present invention contains a hydrolysis inhibitor for the purpose of improving the durability of the resin composition and maintaining its flame retardancy and heat resistance stably for a long period of time. The hydrolysis inhibitor is not particularly limited, and a carbodiimide compound, an epoxy compound, or the like can be used. Among them, a carbodiimide compound can be preferably used from the viewpoint of the hydrolysis inhibition effect.

  The carbodiimide compound is not particularly limited as long as it has one or more carbodiimide groups in the molecule. For example, aliphatic monocarbodiimide, aliphatic polycarbodiimide, alicyclic monocarbodiimide, alicyclic polycarbodiimide, aromatic Group monocarbodiimide, aromatic polycarbodiimide and the like. Furthermore, the carbodiimide compound may have various heterocyclic rings and various functional groups in the molecule.

It does not specifically limit as a method of manufacturing a carbodiimide compound, Many methods, such as the method of manufacturing from an isocyanate compound as a raw material, are mentioned.
As the carbodiimide compound, any of a carbodiimide compound having an isocyanate group in the molecule and a carbodiimide compound having no isocyanate group in the molecule can be suitably used.

  As the carbodiimide skeleton of the carbodiimide compound, 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, 4,4'-dicyclohexylmethanecarbodiimide, tetramethylxylylenecarbodiimide, N, N'- Dimethylphenylcarbodiimide, N, N'-di-2,6-diisopropyl Examples thereof include carbodiimide skeletons such as phenyl carbodiimide.

  There are many specific examples of the carbodiimide compound. Examples of the aliphatic monocarbodiimide include diethyl carbodiimide. Examples of the aliphatic polycarbodiimide include polycarbodiimide derived from ethylene diisocyanate. Examples of the alicyclic monocarbodiimide include dicyclohexylcarbodiimide. Examples of the alicyclic polycarbodiimide include polycarbodiimide derived from 4,4′-dicyclohexylmethane diisocyanate. Examples of the aromatic monocarbodiimide include N, N′-diphenylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide, and the like. Examples of the aromatic polycarbodiimide include polycarbodiimide derived from phenylene-p-diisocyanate, and polycarbodiimide derived from 1,3,5-triisopropyl-phenylene-2,4-diisocyanate.

  In polycarbodiimide, both ends of the molecule or any part of the molecule have a molecular structure different from other parts such as having a functional group such as an isocyanate group or branching of the molecular chain. Or you may. Said hydrolysis inhibitor is used individually or in combination of 2 or more.

  Content of the said hydrolysis inhibitor is 0.1-10 mass parts, Preferably it is 0.1-5 mass parts, Most preferably, it is 0.3-3 mass parts. If the amount is less than 0.1 parts by mass, the intended durability cannot be obtained. On the other hand, if it exceeds 10 parts by mass, the color tone is greatly impaired, and the cost is disadvantageous.

  The resin composition of the present invention contains a glycidyl methacrylate-modified core-shell type impact resistance agent for the purpose of imparting impact resistance and durability. By including a glycidyl methacrylate-modified core-shell type impact agent, the glycidyl group reacts with and binds to the carboxyl group at the end of the polylactic acid resin during melting such as kneading and molding, and the deterioration of polylactic acid is promoted by the carboxyl group at the end. Sealed and has a good effect on durability. In addition, since the core component can be expected to enhance the impact resistance improving effect on the polylactic acid resin, both effects can be efficiently exhibited with respect to the content.

  Furthermore, by including a glycidyl methacrylate-modified core-shell impact agent, a synergistic effect with the above-described hydrolysis inhibitor can be obtained, and better durability can be obtained.

  The polymer constituting the core of the glycidyl methacrylate-modified core-shell impact agent may be a polymer having rubber elasticity. Examples of the polymer having rubber elasticity include rubber obtained by polymerizing components such as an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, or an ethylene-propylene component.

  As the copolymer having rubber elasticity constituting the core, since a bad influence on flame retardancy is small, a copolymer using a rubber in which an acrylic component and a silicone component are combined is particularly preferable. Here, the composite indicates a composite or a polymer alloy.

A method for producing a rubber compounded with an acrylic component and a silicone component is not particularly limited as long as it is a known and commonly used method, but the emulsion polymerization method is optimal from the viewpoint of quality stability.
The shell of the glycidyl methacrylate-modified core-shell type impact agent is composed of a polymer having a glycidyl group and a (meth) acryl group. The polymer constituting the shell needs to be a glycidyl methacrylate (MMA) polymer from the viewpoint of affinity with the resin matrix and reactivity. Here, the methacryl group mainly contributes to the affinity with the resin matrix, and the glycidyl group mainly contributes to the reaction with the terminal carboxyl group of polylactic acid.

The glass transition temperature of the polymer constituting the shell is preferably higher than the glass transition temperature of the polymer constituting the core.
The glycidyl methacrylate-modified core-shell impact agent can be used alone or in combination of two or more.

  The content of the glycidyl methacrylate-modified core-shell impact agent is 1 to 15 parts by mass, preferably 3 to 12 parts by mass, out of 100 parts by mass of the resin composition. If the content is less than 1 part by mass, the effect is not sufficiently obtained. If the content exceeds 15 parts by mass, it is disadvantageous in terms of cost, and the content ratio of polylactic acid, which is a plant-derived component, is not good. This is not preferable because it is relatively lowered. Moreover, the bending strength of the resin composition obtained will fall.

  As the glycidyl methacrylate-modified core-shell type impact-resistant agent, a commercially available product can be suitably used, and examples thereof include a product name “METABREN” series “S2200” manufactured by Mitsubishi Rayon Co., Ltd.

  The resin composition of the present invention preferably contains a fluororesin-based anti-drip agent. In addition to suppressing dripping during combustion, the fluororesin-based anti-drip agent has the effect of shortening the after-flame time, and when seeking flame retardance at V-1 or higher, particularly at the V-0 level in the UL94 standard. The effect improves more by using together with glass fiber.

  The content of the fluororesin-based anti-drip agent is preferably 0.1 to 1 part by mass, more preferably 0.2 to 0.5 part by mass, out of 100 parts by mass of the resin composition. If the amount is less than 0.1 parts by mass, the required combustion particle dripping suppressing effect may not be obtained. On the other hand, if it exceeds 1 part by mass, it is not only disadvantageous in cost but also unfavorable in terms of environmental load.

  As the fluororesin-based anti-drip agent, all known and usual ones can be used, and commercially available products can also be suitably used. For example, the product name “FA500C” manufactured by Daikin Co., Ltd., the product name “MM5935EF” manufactured by 3M Co., Ltd., and the product name “Metablene A3700” manufactured by Mitsubishi Rayon Co., Ltd. may be used.

  A (meth) acrylic acid ester compound may be blended in the resin composition of the present invention. The (meth) acrylic acid ester compound is blended for the purpose of promoting crystallization of the resin composition and further improving heat resistance. As the (meth) acrylic acid ester compound, since it has high reactivity with polylactic acid resin, it is difficult for monomers to remain, there is little toxicity, and there is little coloring of the resin, so there are two or more (meth) acrylic groups in the molecule. Or a compound having one or more (meth) acryl groups and one or more glycidyl groups or vinyl groups.

  Specific examples of (meth) acrylic acid ester 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, Copolymers of alkylenes of various lengths, butanediol methacrylate, butanediol active Rate, and the like. Among these, ethylene glycol dimethacrylate and the like are preferable from the viewpoint of the crystallization promoting effect. These (meth) acrylic acid ester compounds are used alone or in combination of two or more.

  The (meth) acrylic acid ester compound can be blended into the resin composition by a method such as melt kneading with a polylactic acid resin. It is preferable that the compounding quantity of a (meth) acrylic acid ester compound is 0.01-20 mass parts among 100 mass parts of resin compositions, More preferably, it is 0.02-5 mass parts. If the blending amount is less than 0.01 parts by mass, sufficient heat resistance may not be obtained, and if it exceeds 20 parts by mass, the operability during kneading may be reduced.

  When the (meth) acrylic acid ester compound is blended in the resin composition, it is preferable that a peroxide is blended together with the (meth) acrylic acid ester compound. The peroxide is blended for the purpose of promoting the reaction between the polylactic acid resin and the (meth) acrylic ester compound and improving the heat resistance.

  Specific examples of the peroxide include benzoyl peroxide, bis (butylperoxy) trimethylcyclohexane, bis (butylperoxy) cyclododecane, butylbis (butylperoxy) valerate, dicumyl peroxide, butylperoxybenzoate, Examples include dibutyl peroxide, bis (butylperoxy) diisopropylbenzene, dimethyldi (butylperoxy) hexane, dimethyldi (butylperoxy) hexyne, and butylperoxycumene. Among these, dibutyl peroxide is preferable from the viewpoint of heat resistance improvement effect. These peroxides can be used alone or in combination of two or more.

  0.1-20 mass parts is preferable among 100 mass parts of resin compositions, and, as for the compounding quantity of the said peroxide, More preferably, it is 0.1-5 mass parts. If the blending amount is less than 0.1 parts by mass, sufficient heat resistance may not be obtained. On the other hand, if it exceeds 20 parts by mass, the operability during kneading may be reduced. In addition, since a peroxide decomposes | disassembles and is consumed at the time of mixing with resin, it may not remain | survive in the obtained resin composition.

  As long as the properties of the resin composition are not significantly impaired, known additions such as pigments, heat stabilizers, antioxidants, weathering agents, plasticizers, lubricants, mold release agents, and antistatic agents are added to the resin composition of the present invention. An agent can be added. In addition, the method of adding these additives to the resin composition of the present invention is not particularly limited.

  Among these, examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.

Polylactic acid resin and organic phosphinic acid metal salt flame retardant, glass fiber, hydrolysis inhibitor, organic sulfonic acid barium salt and glycidyl methacrylate modified core-shell impact agent, fluororesin anti-drip agent if necessary, (meta) The means for mixing the acrylate compound, peroxide, and other additives is not particularly limited, and examples thereof include a melt kneading method using a uniaxial or biaxial extruder. From the viewpoint of improving 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. If the kneading temperature is lower than the above range, kneading and reaction may be insufficient. On the other hand, if the temperature is higher than the above range, the resin may be decomposed or colored.

  The kneading time is preferably 20 to 1800 seconds. If the kneading time is shorter than the above range, kneading and reaction may be insufficient. On the other hand, if the time is longer than the above range, the resin may be decomposed or colored.

  The resin composition of the present invention can be formed into various molded articles 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, from the viewpoint of productivity, it is preferable to form a molded body by an injection molding method, and in addition to a general injection molding method, gas injection molding, injection press molding, or the like can be adopted.

  In the present invention, if an example of suitable injection molding conditions is given, the cylinder temperature is preferably equal to or higher than the melting point or flow start temperature of the resin composition, and more preferably in the range of 190 to 270 ° C. The mold temperature is preferably (melting point of the resin composition −20) ° C. or less, and more preferably in the range of 80 to 120 ° C. If the cylinder temperature and the mold temperature are lower than the above ranges, the operability may become unstable, such as a short circuit occurring in the molded product, or may be easily overloaded. On the contrary, when the cylinder temperature and the mold temperature are higher than the above ranges, the resin composition is decomposed during the molding process, resulting in a problem that the strength of the resulting molded body is reduced or colored. There is.

  Specific examples of molded articles using the resin composition of the present invention include various parts and casings around personal computers, cellular phone parts and casings, other resin parts for electrical appliances such as OA equipment parts, bumpers, and instrument panels. Resin parts for automobiles such as 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.

Among them, the resin composition of the present invention is particularly useful in parts that require flame retardancy, moldability, bending physical properties (flexibility), impact resistance, heat resistance, and heat and humidity resistance.
The flame retardancy of the resin composition of the present invention is preferably one that achieves a level of V-0 or higher in the UL 94 flame retardancy test. Moreover, as heat resistance, it is preferable that the heat distortion temperature measured by load 1.8MPa based on ISO75-1 is 120 degreeC or more.

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) Formability At the time of molding, the total of the injection time and the time during which pressure is applied after injection is 30 seconds, and then the molded body can be fixed to the mold or taken out without resistance, and deformation due to the ejection pin The time (seconds) required until the mold could be released well was measured and evaluated according to the following criteria.
A: Required time is 20 seconds or less.
A: The required time is longer than 20 seconds and not longer than 25 seconds.
○: The required time is longer than 25 seconds and not longer than 40 seconds.
X: The required time is longer than 40 seconds.
In the present invention, those having a value of ◯ or more are considered to be practically usable.

(2) Flame retardance Measured according to UL94 standard. A test piece having a thickness of 1.6 mm was used. For those where no drip (ie, dripping of flame) was observed during the combustion test, the average of the afterflame time (the sum of the time of the first flame contact and the time of the second flame contact) in each test piece during the combustion test Was calculated and evaluated according to the following criteria.
A: The average afterflame time is 1 second or less.
○: The average afterflame time is longer than 1 second and shorter than 4 seconds.
X: The average afterflame time is 4 seconds or more.
In the present invention, in order to achieve flame retardancy of V-0 level or higher, those having a value of ◯ or higher can be practically used.

(3) Bending strength The bending strength was measured in accordance with ISO 178. Evaluation was made according to the following criteria.
A: Bending strength is 125 MPa or more.
○: Bending strength is greater than 115 MPa and less than 125 MPa.
X: Bending strength is 115 MPa or less.
In the present invention, those marked with ◎ are assumed to be practically usable.

(4) Bending fracture strain The bending fracture strain was measured according to ISO 178. Evaluation was made according to the following criteria.
A: Bending fracture strain is 3 or more.
○: Bending fracture strain is greater than 2 and less than 3.
X: Bending fracture strain is 2 or less.
In the present invention, those marked with ◎ are assumed to be practically usable.

(5) Impact resistance Izod impact strength was measured according to ASTM D256. Evaluation was made according to the following criteria.
A: Izod impact strength is 60 J / m or more.
○: Izod impact strength is greater than 40 J / m and less than 60 J / m.
X: Izod impact strength is 40 J / m or less.
In the present invention, those marked with ◎ are assumed to be practically usable.

(6) Heat resistance Based on ISO 75, the heat distortion temperature was measured under a load of 1.8 MPa (that is, a large load). Evaluation was made according to the following criteria.
(Double-circle): Thermal deformation temperature is 140 degreeC or more.
○: Thermal deformation temperature is 120 ° C or higher and lower than 140 ° C.
Δ: Thermal deformation temperature is higher than 100 ° C and lower than 120 ° C.
X: Heat distortion temperature is 100 degrees C or less.
In the present invention, those having a value of ◯ or more are considered to be practically usable.

(7) Moist heat resistance (bending strength retention)
Two test pieces were prepared, and one was measured for bending strength by the same method as in (3) above. The other one was left to stand for 700 hours in an environment of a temperature of 60 ° C. and a humidity of 95% RH, and was subjected to wet heat treatment, and the bending strength (bending strength after wet heat treatment) was measured by the same measurement method as in (3) above. The bending strength retention was calculated from the following formula.
(Bending strength retention) (Unit:%) = (Bending strength after wet heat treatment) / (Bending strength before wet heat treatment) × 100
Evaluation was made according to the following criteria.
A: Bending strength retention is 70% or more.
○: Bending strength retention is 50% or more and less than 70%.
X: Bending strength retention is less than 50%.
In the present invention, those having a value of ◯ or more are considered to be practically usable.

(8) Moist heat resistance (bending fracture strain retention)
Two test pieces were prepared, and one was measured for bending fracture strain by the same method as in (4) above. The other one is left for 700 hours in a temperature of 60 ° C. and humidity of 95% RH and subjected to wet heat treatment, and the bending fracture strain (bending fracture strain after wet heat treatment) is measured by the same measurement method as in (4) above. did. The bending fracture strain retention rate was calculated from the following formula.
(Bending fracture strain retention) (unit:%) = (bending fracture strain after wet heat treatment) / (bending fracture strain before wet heat treatment) × 100
Evaluation was made according to the following criteria.
A: Bending strength retention is 70% or more.
○: Bending strength retention is 50% or more and less than 70%.
X: Bending strength retention is less than 50%.
In the present invention, those having a value of ◯ or more are considered to be practically usable.

Various raw materials used in Examples and Comparative Examples are as follows.
(1) Product name “3001D” (polylactic acid resin, manufactured by Cargill Dow) (D-form content: 1.4 mol%, MFR: 10 g / 10 min, melting point: 160 to 180 ° C.)
・ Product name “S-12” manufactured by Toyota (D-form content: 0.1 mol%, MFR: 8 g / 10 min, melting point: 160 to 180 ° C.)
(2) Flame Retardant ・ Clariant Organic Phosphinic Acid Metal Salt Flame Retardant (trade name “OP1312”)
・ Ammonium polyphosphate flame retardant (trade name “AP422”) manufactured by Clariant
(3) Product name “FT592” manufactured by Owens Corning
(4) Fluororesin anti-drip agent, product name “FA500C” manufactured by Daikin
・ Product name “MM5935EF” manufactured by 3M
・ Product name “A3700” manufactured by Mitsubishi Rayon Co., Ltd.
(5) Barium salt of organic sulfonate, manufactured by Takemoto Yushi Co., Ltd. Trade name “TLA114”
(6) Crystal nucleating agent other than organic sulfonic acid barium salt, Takemoto Yushi Co., Ltd. Organic sulfonic acid potassium crystal nucleating agent (trade name “TLA140”)
・ New Japan Rika Co., Ltd. trimesic acid amide crystal nucleating agent (trade name “TF-1”)
(7) (Meth) acrylic acid ester compound, manufactured by Nippon Oil & Fats Co., Ltd. Ethylene glycol dimethacrylate (trade name “Blemmer PDE-50”) (hereinafter referred to as “EGDM”)
(8) Peroxide / Nippon Yushi Co., Ltd. Di-t-butyl peroxide (trade name "Perbutyl D")
(9) Hydrolysis inhibitor / Nisshinbo Chemical Co., Ltd. isocyanate-modified carbodiimide (trade name “LA-1”) (isocyanate group content 1 to 3%)
・ Carbodiimide (trade name “EN160”) manufactured by Matsumoto Yushi Co., Ltd.
(10) Glycidyl methacrylate-modified core-shell type impact-resistant agent, manufactured by Mitsubishi Rayon Co., Ltd. Glycidyl methacrylate-modified core-shell type silicone / acrylic rubber-based impact-resistant agent (trade name “METABBRENE S2200”)
(11) Glycidyl methacrylate-containing polymer ・ Nippon Yushi Co., Ltd. Ethylene glycidyl methacrylate / acrylonitrile styrene graft copolymer (trade name “Modiper A4400”)
Example 1
Of 100 parts by mass of the resin composition, 49.6 parts by mass of 3001D as a polylactic acid resin, 28 parts by mass of OP1312 as a flame retardant, 1.0 part by mass of TLA144 as an organic sulfonic acid barium salt, a fluororesin-based anti-drip agent As follows: 0.5 parts by weight of FA500C, 1.3 parts by weight of LA-1 as a hydrolysis inhibitor and 1.3 parts by weight of EN160, 5 parts by weight of S2200 as a glycidyl methacrylate-modified core-shell impact agent, It supplied from the root supply port of the twin-screw extruder (trade name “TEM26SS” manufactured by Toshiba Machine Co., Ltd.). Extrusion was carried out while venting under the conditions of a barrel temperature of 180 ° C., a screw rotation speed of 150 rpm, and a discharge speed of 20 kg / h. At this time, FT592 was supplied as glass fiber from the side into the 13 parts by mass cylinder. At the same time, 0.1 part by mass of EGDM as a (meth) acrylic acid ester compound and 0.2 part by mass of perbutyl D as a peroxide were injected from the side into the cylinder with respect to the total amount of the resin composition.

  The resin discharged from the tip of the extruder was cut into pellets to obtain pellets of the resin composition. The obtained pellet was dried with hot air at 70 ° C. for 24 hours using (Matsui Seisakusho hot air dryer P0-80), and then with an injection molding machine (IS-80G type injection molding machine manufactured by Toshiba Machine Co., Ltd.) A test piece for general physical property measurement (ASTM type) was prepared at a mold surface temperature of 105 ° C. and subjected to various measurements.

(Examples 2 , 4 to 11, Reference Example 1 and Comparative Examples 1 to 8)
Polylactic acid resin, flame retardant, glass fiber, crystal nucleating agent, anti-drip agent, hydrolysis inhibitor, glycidyl methacrylate modified core-shell impact agent, (meth) acrylic acid ester compound, presence or absence of peroxide, blending amount or type Were changed as shown in Table 1 and Table 2, and the same operation as in Example 1 was performed to obtain a resin composition. Next, pellets of the respective resin compositions were obtained in the same manner as in Example 1. After the pellets were injection molded in the same manner as in Example 1, test pieces were prepared and subjected to various measurements.
Table 1 shows the results of Examples and Reference Examples , and Table 2 shows the results of Comparative Examples.

表１から明らかなように、実施例１〜２、４〜１１、参考例１においては、難燃性、耐衝撃性、柔軟性、耐熱性、耐久性、成形性が何れも優れた結果が得られた。実施例のうち、実施例２はフッ素樹脂系ドリップ防止剤が含有されていなかったため、実施例１と比較して、難燃性（残炎時間）に改善の余地を残す結果となった。

As is clear from Table 1, in Examples 1 to 2, 4 to 11 and Reference Example 1 , all the results were excellent in flame retardancy, impact resistance, flexibility, heat resistance, durability, and moldability. Obtained. Among the examples, since the fluororesin drip inhibitor was not contained in Example 2, the result was that there was room for improvement in flame retardancy (residual flame time) compared to Example 1.

In Reference Example 1 , an organic phosphinic acid metal salt flame retardant was not used as a flame retardant, but an ammonium polyphosphate flame retardant was used. Therefore, compared with Example 1, the flame retardancy (residual flame time) was improved. As a result, there was room for room.

In Example 5, since a (meth) acrylic acid ester compound and a peroxide were not used, compared with Example 1, it resulted in leaving the room for improvement in a moldability.
In Example 11, since the polylactic acid resin in which the ratio of the D-form component in the molecular chain was 0.6 mol% or less was used as the polylactic acid resin, a result that was remarkably excellent in moldability was obtained.

On the other hand, in Comparative Examples 1 and 2, since a crystal nucleating agent other than the organic sulfonic acid barium salt was used, the moldability was excellent, but the flame retardancy was inferior.
In Comparative Example 3, since no organic sulfonic acid barium salt was used, the results were inferior in heat resistance and moldability.

In Comparative Example 4, since the amount of the flame retardant was small, the result was inferior in flame retardancy.
In Comparative Example 5, since the glass fiber content was small, the flame retardancy was inferior, and drip was observed during the combustion test.

In Comparative Example 6, the content of the organic sulfonic acid barium salt was small, resulting in poor heat resistance and moldability.
In Comparative Example 7, since the content of the hydrolysis inhibitor was small, the result was inferior in heat and humidity resistance.

In Comparative Example 8, since the glycidyl methacrylate-modified core-shell impact agent was not used, the impact resistance was inferior.
In Comparative Example 9, the amount of the flame retardant was too large, resulting in inferior strength, breaking strain, and impact resistance.

In Comparative Example 10, since the compounding amount of the organic sulfonic acid barium salt was too large, the results were inferior in breaking strain and impact resistance.
In Comparative Example 11, since the blending amount of the glycidyl methacrylate-modified core-shell type impact agent was too large, the bending strength was inferior.

  In Comparative Example 12, a glycidyl methacrylate-containing polymer was blended, but the result was inferior in impact resistance because it was not a core-shell impact agent.

Claims (6)

Of the total 100 parts by mass, the polylactic acid resin is 25 to 85 parts by mass, the organic phosphinic acid metal salt flame retardant is 10 to 40 parts by mass, the glass fiber is 5 to 55 parts by mass, and the hydrolysis inhibitor is 0.1 to 0.1 parts by mass. A flame-retardant resin composition comprising 10 parts by mass, 0.03 to 5 parts by mass of an organic sulfonic acid barium salt, and 1 to 15 parts by mass of a glycidyl methacrylate-modified core-shell type impact agent. The flame retardant resin composition according to claim 1, comprising 0.1 to 1 part by mass of a fluororesin-based anti-drip agent. The flame retardant resin composition according polylactic acid resin to claim 1 or 2, characterized in that it contains more than 50 parts by weight. The flame retardant according to any one of claims 1 to 3 , which is melt-kneaded together with 0.01 to 20 parts by weight of a (meth) acrylic ester compound and 0.1 to 20 parts by weight of a peroxide. Resin composition. The flame retardant resin composition according to any one of claims 1 to 4 , wherein the ratio of the D-form component in the polylactic acid resin is 0.6 mol% or less. It is a manufacturing method of a flame-retardant resin composition, Comprising: Of all 100 mass parts, 25-85 mass parts of polylactic acid resin, 10-40 mass parts of organic phosphinic acid metal salt flame retardants, 5-55 glass fibers 0.1 to 10 parts by mass of a hydrolysis inhibitor, 0.03 to 5 parts by mass of an organic sulfonic acid barium salt, and 1 to 15 parts by mass of a glycidyl methacrylate-modified core-shell impact agent. A method for producing a flame retardant resin composition.