JP2012072351A - Polysiloxane-modified polylactic acid resin composition and manufacturing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysiloxane-modified polylactic acid resin composition that exhibits high-grade flame retardancy and thermal conductivity as well as excellent impact resistance and flexibility.SOLUTION: The polysiloxane-modified polylactic acid resin composition comprises a polylactic acid resin, a thermal conductivity-imparting agent and expandable graphite, where the polylactic acid resin has a segment of a polylactic acid compound and a segment of an amino group-bearing polysiloxane compound bearing an amino group in its side chain with the amino group content within the range of 0.01-2.5 mass% based on the amino group-bearing polysiloxane compound and the amino group compounded amount within the range of 3-300 mass ppm based on the polylactic acid compound.

Description

  The present invention relates to a polysiloxane-modified polylactic acid resin composition and a method for producing the same.

  Polyhydroxycarboxylic acids such as polylactic acid have relatively excellent moldability, toughness, rigidity, and the like. Among them, polylactic acid can be synthesized from natural raw materials such as corn, and has excellent molding processability, biodegradability, and the like, and therefore has been developed in various fields as an environmentally friendly resin.

  However, polylactic acid is generally flammable. For example, when used in applications that require high flame retardancy, such as home appliances, OA equipment housings, and automobile parts, flame retardant measures is required. For example, when a polylactic acid resin is used for a housing of an electrical product, it is necessary to satisfy a flame retardant standard such as the US UL standard.

  In addition, polylactic acid, while having excellent physical properties, is inferior in flexibility, such as impact resistance, bending bending strain, and tensile breaking strain, compared to resins made from petroleum such as ABS resin, and therefore has high resistance to It is difficult to use for exterior materials for electric and electronic devices that require impact.

  Furthermore, in recent electrical and electronic equipment applications, thermal conductivity is required to efficiently dissipate heat generated from various devices. Thermoplastic resins and thermosetting resins are generally thermally conductive. Is not enough. Such a resin material with poor thermal conductivity may prevent heat dissipation and induce failure or destruction in these devices and elements when they are applied to parts such as electronic devices and housing materials.

  For the purpose of improving impact resistance, flame retardancy, etc., a biodegradable resin composition containing polylactic acid and silicone / lactic acid copolymer has been proposed (Patent Document 1). However, this biodegradable resin composition involves a complicated process for producing a silicone / lactic acid copolymer. In addition, although this biodegradable resin composition has good flame retardancy, it has insufficient impact resistance compared to resins that have been used in conventional electronic and electrical equipment applications, and is applied to practical products. Is disadvantageous.

  For the purpose of improving flame retardancy and impact resistance, a resin composition containing a polylactic acid resin, a thermoplastic resin other than a lactic acid resin, phosphonitrile phenyl ester, and expandable graphite has been proposed. (Patent Document 2). However, this resin composition has a low initial Izod impact strength before the wet heat test, and does not reach a practical level in applications requiring large toughness (impact resistance) such as home appliances, OA equipment housings, and automobile parts. There is a case.

  For the purpose of improving mechanical strength and thermal conductivity, a polylactic acid resin in which carbon fibers are kneaded has been proposed (Patent Document 3). However, this polylactic acid-based resin may cause problems such as a decrease in mechanical strength due to the blending of low molecular weight polylactic acid and bleeding of organic compounds having a low affinity with polylactic acid. Since it is not provided, it could not be widely used in the electric and electronic fields where high flame retardancy is required.

  In addition, for the purpose of improving heat resistance, mechanical strength, hydrolysis resistance, and environmental compatibility, a resin composition containing a polylactic acid resin, a polycarbonate resin, and an amine group-containing chain extender has been proposed (Patent Literature). 4). In this resin composition, the polylactic acid resin is increased in viscosity with an amino group-containing chain extender, and the desired physical properties are achieved by controlling the morphology with the polycarbonate resin. However, this resin composition inhibits the high fluidity characteristic of polylactic acid resins and is not suitable for thin-wall molding. Furthermore, this resin composition is inferior in environmental harmony since petroleum-derived polycarbonate resin is an essential component.

JP 2004-277575 A JP 2008-274224 A JP 2005-138458 A JP 2009-293031 A

  Therefore, the present invention provides a polysiloxane-modified polylactic acid resin composition having high flame retardancy and thermal conductivity, and further having excellent impact resistance and flexibility, and a method for producing the same. Objective.

In order to achieve the above object, the polysiloxane-modified polylactic acid resin composition of the present invention comprises:
Including a polylactic acid-based resin, a thermal conductivity imparting agent and expandable graphite,
The polylactic acid resin is
A segment of polylactic acid compound,
A segment of an amino group-containing polysiloxane compound having an amino group in the side chain,
The content of the amino group with respect to the amino group-containing polysiloxane compound is in the range of 0.01% by mass to 2.5% by mass,
The compounding quantity of the said amino group with respect to the said polylactic acid-type compound is the range of 3 mass ppm-300 mass ppm, It is characterized by the above-mentioned.

The method for producing the polysiloxane-modified polylactic acid resin composition of the present invention comprises:
Mixing and stirring an amino group-containing polysiloxane compound having an amino group in the side chain and a polylactic acid-based compound in a molten state, and further mixing and stirring a thermal conductivity-imparting agent and expandable graphite;
The content of the amino group with respect to the amino group-containing polysiloxane compound is in the range of 0.01% by mass to 2.5% by mass,
The compounding quantity of the said amino group with respect to the said polylactic acid-type compound is the range of 3 mass ppm-300 mass ppm, It is characterized by the above-mentioned.

  The polysiloxane-modified polylactic acid resin composition of the present invention has high flame retardancy and thermal conductivity, and further has excellent impact resistance and flexibility.

It is a figure which shows the thermography (thermal conductivity) of the polysiloxane modified polylactic acid-type resin composition in the Example of this invention in comparison with stainless steel.

  The present inventors diligently studied to impart a high degree of flame retardancy and thermal conductivity to the polylactic acid-based resin, and to improve flexibility such as excellent impact resistance and good breaking bending strain and tensile breaking strain. As a result, the polylactic acid-based resin obtained by reacting the polylactic acid-based compound with the amino group-containing polysiloxane compound has excellent impact resistance, flexibility such as good breaking bending strain and tensile breaking strain. I found out. In addition, by adding a thermal conductivity imparting agent (for example, carbon fiber, copper-plated aramid fiber, metal fiber, etc.) and expandable graphite to the polylactic acid-based resin, excellent impact resistance, good breaking bending strain and It has been found that excellent thermal conductivity and flame retardancy can be obtained while maintaining flexibility such as tensile breaking strain.

  The reason why the polysiloxane-modified polylactic acid resin composition of the present invention exhibits particularly excellent mechanical properties such as impact resistance is that the amino group-containing polysiloxane compound segment, the polylactic acid compound segment, This is considered to be because a polysiloxane / polylactic acid copolymer is formed by the bonding. Due to the presence of this polysiloxane / polylactic acid copolymer, the molded article using the polysiloxane-modified polylactic acid resin composition of the present invention has excellent impact resistance, good breaking bending strain and tensile breaking strain, etc. It is thought that flexibility can be imparted. The polysiloxane / polylactic acid copolymer is considered to be produced by a reaction between the amino group-containing polysiloxane compound and the ester group of the polylactic acid compound. Moreover, thermal conductivity-imparting agents such as carbon fibers and expandable graphite have a low surface polarity, so they are not easily compatible with highly polar polylactic acid compounds, but are very easily compatible with polysiloxane compounds. For this reason, the polysiloxane / polylactic acid copolymer promotes the dispersion of the thermal conductivity-imparting agent and the expandable graphite, suppresses a decrease in strength due to phase separation and a decrease in interfacial strength, and has excellent impact resistance and fracture. It is thought that it has excellent thermal conductivity while maintaining bending strain and tensile breaking strain. Furthermore, this excellent thermal conductivity promotes the expansion of the expandable graphite during combustion and efficiently forms a heat insulating layer, so it is considered that a high level of flame retardancy can be achieved. Furthermore, the polysiloxane-modified polylactic acid resin composition of the present invention is also excellent in bleed resistance. Originally, the polylactic acid compound and the polysiloxane compound have poor compatibility and are liable to cause poor dispersibility and bleeding, but the polysiloxane modified polylactic acid resin composition of the present invention has a specific amount of amino group. A polysiloxane / polylactic acid copolymer in which a specific amount of a polysiloxane compound is introduced into the polylactic acid compound is formed by a polymerization reaction between the polylactic acid compound and the polylactic acid compound. This polysiloxane / polylactic acid copolymer forms silicone elastomer particles that are well dispersed in the polylactic acid-based resin and that are well bonded to the polylactic acid-based resin interface. For this reason, it is considered that bleed resistance can be imparted to a molded product using the polysiloxane-modified polylactic acid resin composition of the present invention. However, these mechanisms are estimations and do not limit the present invention.

  In the segment of the amino group-containing polysiloxane compound, the amino group is bonded to the side chain of the polysiloxane compound. The amino group-containing polysiloxane compound having an amino group in the side chain is easy to adjust the concentration of the amino group and easily adjust the reaction with the segment of the polylactic acid compound. In particular, if the amino group is a diamino group, the reactivity with the polylactic acid compound is higher than that of the monoamino group, which is preferable.

  The content of the amino group relative to the amino group-containing polysiloxane compound is such that the molecular weight of the amino group-containing polysiloxane compound is increased while maintaining the reactivity with the segment of the polylactic acid compound, It is necessary to make the range within which volatilization of the group-containing polysiloxane compound can be suppressed. The content of the amino group is in the range of 0.01% by mass to 2.5% by mass, and preferably in the range of 0.01% by mass to 1.0% by mass. If the content of the amino group is 0.01% by mass or more, the polylactic acid compound segment and the amide bond can be sufficiently formed and efficiently produced, and the molded product can be separated by separating the polysiloxane segment. Bleed out can be suppressed. If the content of the amino group is 2.5% by mass or less, the hydrolysis of the polylactic acid compound at the time of production is suppressed, the aggregation is suppressed, the mechanical strength is high, and the molding has a uniform composition. Goods are obtained.

The content of the amino group can be determined by the following formula (I).

Content of amino group (mass%) = (16 / amino equivalent) × 100 (I)
Amino equivalent: Average value of the mass of the amino group-containing polysiloxane compound per mole of amino groups (g / mol)

  Moreover, the compounding quantity of the said amino group with respect to the said polylactic acid type compound is the range of 3 mass ppm-300 mass ppm, Preferably, it is the range of 50 mass ppm-300 mass ppm. If the compounding amount of the amino group is 3 mass ppm or more, it is possible to improve the impact resistance due to the segment of the amino group-containing polysiloxane compound in the molded product. If the compounding amount of the amino group is 300 ppm by mass or less, it is easy to disperse the polylactic acid compound and the amino group-containing polysiloxane compound during production, and the molecular weight of the polylactic acid resin is significantly reduced. And a molded product having excellent mechanical strength such as impact strength can be obtained.

The compounding amount of the amino group can be obtained by the following formula (II).

Amino group content (mass ppm) =
Amino group content (% by mass) with respect to the amino group-containing polysiloxane compound ×
Ratio of amino group-containing polysiloxane compound to polylactic acid compound (% by mass) ×
100 (II)

As the amino group-containing polysiloxane compound constituting such a segment, a compound that easily binds to the segment of the polylactic acid compound under mild conditions without using special means is preferable. Examples of such amino group-containing polysiloxane compounds include those represented by the following formula (1) and the following formula (2).
In the above formulas (1) and (2),
R _{4 to} R ₈ , R _{4 ′} , R _{10 to} R ₁₄ and R _{10 ′} are each an alkyl group having 18 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, — (CH ₂ ) _α —NH—C ₆ H ₅ (α is an integer of 1 to 8), which may be wholly or partially substituted with a halogen atom, and R _{4 to} R ₈ , R _{4 ′} , R ₁₀ ~ R ₁₄ and R _{10 '} may be the same or different,
R ₉ , R ₁₅ and R ₁₆ each represent a divalent organic group, and R ₉ , R ₁₅ and R ₁₆ may be the same or different,
d ′ and h ′ each represent an integer of 0 or more;
e and i each represents an integer of 1 or more.

As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, and the like are preferable. The alkenyl group is preferably a vinyl group. As said aryl group, a phenyl group, a naphthyl group, etc. are preferable. Examples of the alkylaryl group include a benzyl group. Examples of the halogen atom include chlorine, fluorine, bromine and the like. Specific examples of the halogen substituent include a chloromethyl group, a 3,3,3-trifluoromethyl group, a perfluorobutyl group, and a perfluorooctyl group. R _{4 to} R ₈ , R _{4 ′} , R _{10 to} R ₁₄ and R _{10 ′} are particularly preferably a methyl group or a phenyl group.

  The phenyl group has a function of improving the transparency of the segment of the polysiloxane compound. The refractive index of the polylactic acid resin can be adjusted by adjusting the content of the phenyl group. By making the refractive index of the segment of the polysiloxane compound coincide with the refractive index of the segment of the polylactic acid compound, a uniform refractive index can be obtained in the molded product, and desired transparency is imparted to the molded product. be able to.

Examples of the divalent organic group include an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group, an alkylarylene group such as a phenylene group and a tolylene group, and — (CH ₂ —CH ₂ —O) _b — (b Is an integer of 1 to 50), — [CH ₂ —CH (CH ₃ ) —O] _c — (c is an integer of 1 to 50) or the like, or a polyoxyalkylene group, — (CH ₂ ) _d- NHCO- (d is an integer of 1-8) etc. can be mentioned. Among these, it is particularly preferable that R ₁₆ is an ethylene group and R ₉ and R ₁₅ are propylene groups.

  d ′, h ′, e and i are preferably values in which the number average molecular weight of the polysiloxane compound falls within the range described later. d ′ and h ′ are each preferably an integer of 1 to 15000, more preferably an integer of 1 to 400, and still more preferably an integer of 1 to 100. Each of e and i is preferably in the range of 1 to 15000, and the amino group content relative to the amino group-containing polysiloxane compound determined by the formula (I) is 0.01% by mass to 2.5% by mass. It is necessary to be an integer satisfying the range.

  In the amino group-containing polysiloxane compounds represented by the above formulas (1) and (2), the repeating units each repeated by the number of repeating units d ′, h ′, e and i are the same repeating units connected in succession. Alternatively, they may be connected alternately or randomly.

  The number average molecular weight of the amino group-containing polysiloxane compound is preferably in the range of 900 to 120,000. When the number average molecular weight is 900 or more, loss due to volatilization during kneading with a molten polylactic acid compound can be suppressed during the production of the polylactic acid resin. If the number average molecular weight is 120,000 or less, a uniform molded article having good dispersibility can be obtained. The number average molecular weight is more preferably in the range of 900-20000, and still more preferably in the range of 900-8000.

  As the number average molecular weight, for example, a measurement value measured by GPC (calibration with polystyrene standard sample) analysis of a 0.1% chloroform solution of the sample can be adopted.

In the polysiloxane-modified polylactic acid-based composition of the present invention, it is preferable that the segment of the amino group-containing polysiloxane compound includes a segment composed of a reaction product with an epoxy group-containing polysiloxane compound having an epoxy group. Thereby, it is possible to obtain a polysiloxane-modified polylactic acid resin composition having more excellent impact resistance, flexibility such as good breaking bending strain and tensile breaking strain, and excellent bleeding resistance. This is presumably because stronger silicone elastomer particles are formed in the polysiloxane / polylactic acid copolymer to impart plasticity. However, this mechanism is an estimation and does not limit the present invention. Specifically, the epoxy group-containing polysiloxane compound constituting the segment is preferably a compound represented by the following formula (12), the following formula (19), the following formula (20), or the following formula (21).
In the above formulas (12), (19), (20) and (21),
R ₁ , R ₂ and R _{18 to} R ₂₁ are each an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, — (CH ₂ ) _α -NH—C ₆ H ₅ ( α represents an integer of 1 to 8), which may be wholly or partially substituted with a halogen atom, and R ₁ , R ₂ and R _{18 to} R ₂₁ may be the same or different;
R ₃ represents a divalent organic group,
l ′ and n ′ each represents an integer of 0 or more,
m represents an integer of 1 or more.

The alkyl group, the alkenyl group, the aryl group, the aralkyl group, the alkylaryl group, and — (CH ₂ ) _α —NH—C ₆ H ₅ are represented by R ₄ or the like in the formula (1). Examples of the divalent organic group include those having the same meaning as those represented by R _{9 and the} like in the formula (1).

  Furthermore, the epoxy group content of the epoxy group-containing polysiloxane compound represented by the formula (19) and the formula (21) is preferably less than 2% by mass. By making the epoxy group content less than 2% by mass, the reaction with the amino group-containing polysiloxane compound can be controlled, and by forming a moderately crosslinked elastomer, the mechanical properties are improved. A molded product can be obtained.

  The number average molecular weight of the epoxy group-containing polysiloxane compound is preferably in the range of 900 to 120,000 for the same production reason as in the case of the amino group-containing polysiloxane compound.

The epoxy group content of the epoxy group-containing polysiloxane compound can be determined by the following mathematical formula (III).

Epoxy group content (% by mass) = (43 / epoxy equivalent) × 100 (III)
Epoxy equivalent: mass of polysiloxane compound per mole of epoxy group (g / mol)

  The content of the epoxy group-containing polysiloxane compound constituting the segment of the amino group-containing polysiloxane compound is preferably in the range of 0% by mass to 10% by mass with respect to the segment of the polylactic acid compound. More preferably, it is in the range of 5% by mass to 5% by mass. If content of the said epoxy group containing polysiloxane compound is 10 mass% or less, it can suppress that the epoxy group containing polysiloxane compound which remains without reacting with an amino group bleeds out from a molded article.

  The amino group-containing polysiloxane compound segment may include a segment of a polysiloxane compound having an amino group at the end of the main chain as long as the function of the amino group-containing polysiloxane compound is not impaired. A segment such as a polysiloxane compound not containing an amino group may be included. The content of the polysiloxane compound having an amino group at the end of the main chain and the polysiloxane compound not containing the amino group is in the range of 0% by mass to 5% by mass in the amino group-containing polysiloxane compound. preferable. The number average molecular weight of the polysiloxane compound having an amino group at the end of the main chain and the polysiloxane compound not containing the amino group is preferably in the range of 900 to 120,000.

As the segment of the polylactic acid compound, an extract of a polylactic acid compound obtained from a biomass raw material, a derivative or modified product thereof, a monomer, an oligomer of a lactic acid compound obtained from a biomass raw material, or a derivative thereof Or the segment of the polylactic acid-type compound synthesize | combined using raw materials other than a biomass raw material other than the polycondensate synthesized using a modified body can be mentioned. Examples of the polylactic acid compound constituting the segment include a compound represented by the following formula (27).
In the formula (27),
R ₁₇ represents an alkyl group having 18 or less carbon atoms,
a and c represent an integer of 1 or more;
b ′ represents an integer of 0 or more.

  It is preferable that a is an integer of 500-13000, More preferably, it is an integer of 1500-4000. b ′ is preferably an integer of 0 to 5000. c is preferably an integer of 1 to 50. In the polylactic acid compound represented by the formula (27), the repeating units that are respectively repeated by the repeating unit numbers a and b ′ are alternately repeated even if the same type of repeating units are continuously connected. May be. Specific examples of the polylactic acid compound represented by the formula (27) include polymers of L-lactic acid, D-lactic acid and derivatives thereof, and copolymers having these as main components. Can do. Examples of such copolymers include L-lactic acid, D-lactic acid and derivatives thereof, for example, glycolic acid, polyhydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate, polybutylene adipate terephthalate, polybutylene succinate. Mention may be made of copolymers obtained from one or more of terephthalate, polyhydroxyalkanoate and the like. Among these, from the viewpoint of saving petroleum resources, those derived from plants are preferred. From the viewpoint of heat resistance and moldability, poly (L-lactic acid), poly (D-lactic acid) and their co-products are preferred. Polymers are particularly preferred. Polylactic acid mainly composed of poly (L-lactic acid) has a melting point of 160 ° C. or higher in consideration of mechanical properties and heat resistance of the molded product, although the melting point varies depending on the ratio of the D-lactic acid component. Is preferred.

  The molecular weight of the polylactic acid compound is preferably in the range of 30,000 to 1,000,000, more preferably in the range of 100,000 to 300,000.

  Examples of the thermal conductivity-imparting agent include carbon fibers, boron nitride, boron nitride fibers, copper-plated aramid fibers, and stainless steel fibers. Among these, carbon fibers are particularly preferable. The content of the thermal conductivity-imparting agent is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 5% by mass to 20% by mass with respect to the polysiloxane-modified polylactic acid resin composition. It is. When the content of the thermal conductivity-imparting agent is 1% by mass or more, sufficient thermal conductivity can be obtained in the molded body. If the content of the thermal conductivity imparting agent is 40% by mass or less, for example, even in a polysiloxane-modified polylactic acid-based resin composition containing particularly low-density carbon fibers, the increase in volume fraction is suppressed, An increase in the melt viscosity of the composition due to the entanglement between the carbon fibers can be suppressed, and excellent moldability can be obtained. The copper-plated aramid fiber and stainless steel fiber are commercially available in a compound in which these fibers are blended at a high concentration in plastic, and the addition of the thermal conductivity-imparting agent in the present invention may be performed using the compound. .

  The carbon fiber is a carbon fiber having an average layer spacing (d002) of (002) planes determined by X-ray diffraction of 0.3367 nm or more and less than 0.3440 nm and a crystallite size Lc in the C-axis direction of 10 nm to 35 nm. It is preferable that the thermal conductivity can be imparted to the polysiloxane-modified polylactic acid resin composition. The average layer spacing (d002) of (002) planes determined by the X-ray diffraction is a distance between carbon layer planes in a benzenoid structure in which a network-like carbon layer having a carbon six-membered ring condensation structure is laminated, In the case of graphite whose carbon layer surface is a plane, it is 0.3354 nm.

  The crystallite is a unit that can be regarded as a single crystal constituting one solid particle. One particle constituting a solid is formed by integrating a plurality of crystallites. As the crystallite size increases, the number of crystal lattices increases and the crystallinity increases. The C-axis direction is a direction perpendicular to the carbon layer surface in the benzenoid structure.

  As described above, preferably, the average layer surface spacing (d002) is 0.3367 nm or more and less than 0.3440 nm, and more preferably 0.3390 nm or more and less than 0.3440 nm. If the average layer surface spacing (d002) is 0.3367 nm or more, it is possible to suppress stiffening due to excessive crystallization of the carbon fiber, and thus it is possible to suppress breakage or cutting of the carbon fiber during kneading with the resin or in the molding process. If the average layer surface spacing (d002) is less than 0.3440 nm, the interlayer distance is sufficiently small to form a highly crystalline graphite structure, and heat conduction is improved, so that polysiloxane-modified polylactic acid resin High thermal conductivity can be imparted to the composition. Furthermore, the carbon fiber having an average layer spacing (d002) of 0.3367 nm or more and less than 0.3440 nm can reduce the processing temperature for crystallization (graphitization) to a relatively low temperature of 2500 ° C. or less. Cost can be kept low.

  As described above, the crystallite size Lc is preferably in the range of 10 nm to 35 nm, and more preferably in the range of 10 nm to 20 nm. If the crystallite size Lc is 10 nm or more, the crystallite size Lc is sufficient to obtain high thermal conductivity due to lattice vibration of the crystal lattice, and high thermal conductivity can be imparted to the polysiloxane-modified polylactic acid resin composition. . If the crystallite size Lc is 35 nm or less, it is possible to suppress stiffening due to excessive crystallization of the carbon fiber, and thus it is possible to suppress breakage or cutting of the carbon fiber in the kneading with the resin or in the molding process. Furthermore, the carbon fiber having a crystallite size Lc in the range of 10 nm to 35 nm can reduce the processing energy for crystallization (graphitization) to a relatively low temperature of 2500 ° C. or lower, so that production energy and cost can be kept low. Can do.

Here, for the crystallite size Lc (nm), for example, a value obtained by a wide angle X-ray diffraction method can be adopted. Specifically, a carbon fiber is cut into a length of 4 cm, and is solidified into a prismatic shape using a mold and an alcohol solution of collodion to obtain a sample. CuKα (Ni filter) is used as the X-ray source, and the output is 40 kV and 20 mA. Then, the crystal size is calculated from the half width of the peak of the plane index (002) obtained by the transmission method using the Scherrer equation, Lc (hkl) = K · λ / β0 · cos θB. Here, Lc (hkl) is the average size of crystals in the direction perpendicular to the (hkl) plane, K is 1.0, λ is the wavelength of X-rays, and β0 is (βE ² -β1). ² ) ^1/2 , θB is the Bragg angle, βE is the apparent half width (measured value), and β1 is 1.05 × 10 ⁻² rad.

In addition, as the average layer surface spacing (d002), for example, a value obtained as follows can be adopted. That is, an X-ray diffraction pattern is obtained by using carbon fiber as a powder, filling a sample cell made of aluminum, and using CuKα rays monochromatized by a graphite monochromator as a radiation source. The peak position of the (002) diffraction line is obtained by the centroid method (a method of obtaining the centroid position of the diffraction line and obtaining the peak position using the corresponding 2θ value). 111) Correct using diffraction lines (28.466 °), and calculate d ₀₀₂ from Bragg's formula d ₀₀₂ = λ / 2 · sin θ. Here, the wavelength λ of the CuKα ray is 0.15418 nm.

  The average fiber length of the carbon fibers is preferably a plane orientation, that is, a length capable of forming a two-dimensional network structure in the molded body to be molded, and is preferably in the range of 0.1 mm to 50 mm. The carbon fiber having such an average fiber length is well-familiar with the polysiloxane compound segment of the polylactic acid resin, and the network structure is very easy in the polysiloxane-modified polylactic acid resin composition even at a low content. Can be formed. For this reason, the carbon fibers are in extremely close proximity or in direct contact with each other, the propagation loss of thermal energy is remarkably reduced, and heat conduction can be performed efficiently. In addition, if the average fiber length of the carbon fibers is 50 mm or less, it is possible to suppress mixing and molding with the resin due to the entanglement of the carbon fibers, and to suppress nozzle clogging during injection molding. . Furthermore, since it is easy to orient in the flow direction or the surface direction of the resin at the time of molding, the anisotropic thermal conductivity can be remarkably improved in the obtained molded body as compared with the conventional one. This is because the carbon fibers in the molded body are oriented while maintaining contact or extremely close to each other, and a network structure is formed, so that the effective area of the carbon fibers involved in the contact area between the carbon fibers or the heat conduction thereof. This is thought to be because the area increases and the thermal resistance significantly decreases. However, this mechanism is an estimation and does not limit the present invention.

  As the average fiber length of the carbon fiber, for example, a value obtained by a measuring method such as a microscope method, a laser diffraction / scattering method, or a dynamic light scattering method can be adopted.

  As the carbon fiber, one having an average diameter in the range of 1 μm to 50 μm is preferably used. When the average diameter is 1 μm or more, there is little tendency to agglomerate and it can be easily dispersed in mixing with the resin. When the average diameter is 50 μm or less, the resin can be uniformly dispersed in the resin, and occurrence of poor appearance due to exposure of carbon fiber aggregates on the surface of the molded body can be suppressed. The average diameter of the carbon fiber can be determined by, for example, a microscopic method.

  The carbon fiber preferably has an aspect ratio in the range of 2 to 50000, more preferably in the range of 10 to 50000. The aspect ratio is the ratio of the fiber length to the average diameter of the carbon fibers.

  The carbon fiber preferably has a thermal conductivity of 70 W / m · K to 600 W / m · K. If the carbon fiber has a thermal conductivity in the above range, the carbon fiber has flexibility capable of suppressing breakage during kneading with the resin component, and has sufficient thermal conductivity, so that high thermal conductivity is achieved. The resin composition which has is obtained. Further, since the carbon fiber has a thermal conductivity in the above range, the carbon fiber has a particularly excellent thermal conductivity in the fiber axis direction, and is oriented in the flow direction of the resin by injection molding or the like. It is possible to control the direction and amount of movement of heat.

  As the thermal conductivity, for example, a measured value by a measuring method such as a laser flash method, a flat plate heat flow meter method, a temperature wave thermal analysis method (TWA method), a temperature gradient method (flat plate comparison method) can be adopted.

  As the carbon fiber, one synthesized by pitch system, PAN system, arc discharge method, laser evaporation method, CVD method (chemical vapor deposition method), CCVD method (catalyst chemical vapor deposition method) or the like is used. it can. Of these, carbon fibers obtained by further graphitizing in a pitch system are preferable because of excellent crystallinity and thermal conductivity in the fiber axis direction. In particular, carbon tubes, carbon nanotubes, carbon horns, carbon nanohorns, etc. produced in the mesophase (anisotropic) pitch system and in the gas phase have an anisotropic graphite structure with respect to the fiber axis direction. Compared with carbon fiber having conductivity and an isotropic graphite structure, higher thermal conductivity can be imparted to the polysiloxane-modified polylactic acid resin composition.

  Next, an example is given and demonstrated about the manufacturing method of such a carbon fiber. As the raw material of the carbon fiber, a hydrocarbon compound that is easily graphitized, for example, a condensed polycyclic hydrocarbon compound such as naphthalene or phenanthrene, a condensed heterocyclic compound of petroleum or coal-based pitch, or the like can be used. In particular, by using petroleum pitch, coal pitch, preferably optical anisotropic pitch, that is, mesophase pitch, a highly heat conductive polymer composition and a heat conductive molded body can be obtained. Any mesophase pitch may be used as long as it can be spun, but a mesophase content of 100% is preferable from the viewpoint of high thermal conductivity, spinnability, and quality stability. These raw materials are spun by a conventional spinning method (for example, a melt spinning method, a melt blow method, a centrifugal spinning method, a vortex spinning method, etc.) to obtain pitch-based carbon fibers. Next, a method of heat treatment in an atmosphere of an oxidizing gas such as nitrogen dioxide or oxygen at a relatively low temperature of 200 to 400 ° C., a method of treating in an oxidizing aqueous solution such as nitric acid or chromic acid, polymerization by light or γ-rays, etc. It is set as an infusible fiber using the processing method. Next, a boron compound such as boron carbide, boron oxide or boron nitride, or a graphitization catalyst such as boron alone is added to the infusible fiber, for example, 0.1% by mass to 10% by weight of boron with respect to the carbon fiber. A graphitization treatment is performed by adding an amount such that the mass%. The graphitization temperature is preferably in the range of 1500 ° C to 2500 ° C. If the graphitization temperature is 1500 ° C. or higher, carbon fibers having the crystallite size Lc and the average layer spacing can be produced in a practical processing time. When the graphitization temperature is 2500 ° C. or less, it is possible to suppress the consumption of surplus energy that is input to the heating. The raw material carbon fiber may be used as it is, but if necessary, a part or all of the raw material carbon fiber may be surface-treated.

  As the surface treatment of the raw material carbon fiber, specifically, oxidation treatment, nitridation treatment, nitration, sulfonation, or a functional group introduced into the surface by these treatments or the surface of the carbon fiber, metal, metal compound And a treatment for attaching or bonding an organic compound or the like. Specific examples of the functional group include an oxygen-containing group such as a hydroxyl group, a carboxyl group, a carbonyl group, a nitro group, and an amino group, and a nitrogen-containing group. In the carbon fiber in which such a functional group or compound is introduced into a part of the surface, chemical interaction with the polylactic acid-based resin is strengthened, so that the mechanical strength is improved in the obtained molded body.

  Examples of the surface treatment of the raw carbon fibers include a treatment for bonding or attaching a functional group or compound having an interaction with an organic compound contained in the polysiloxane-modified polylactic acid resin composition to the surface. The carbon fiber subjected to such a surface treatment has a stronger bond with an organic compound and can further improve the thermal conductivity in the molded body. Specific examples include surface treatment with various carboxylic acids and the like.

  Furthermore, the surface treatment can also include a hydrophobic treatment of the carbon fiber surface. Examples of the hydrophobic treatment include a method of performing a heat treatment in an inert gas atmosphere and a fluorination treatment. Such a carbon fiber that has been subjected to a hydrophobization treatment has a stronger interaction with the polysiloxane compound segment of the polylactic acid resin. Moreover, the sizing process using a sizing agent can also be mentioned as said surface treatment.

  As the carbon fiber, a carbon fiber having a fiber length shorter than the average fiber length, for example, a fiber length of 5 nm or more and less than 100 μm, or a carbon compound may be used. As the carbon fiber having a short fiber length, it is preferable to use an aggregate such as a carbon fiber having high crystallinity. Preferred examples of the carbon compound include graphite, expanded graphite, and exfoliated graphite. The average particle size of the carbon compound is preferably in the range of 1 μm to 300 μm because mixing with the components of the polylactic acid resin is easy. The presence of short fiber length carbon fibers and carbon compounds in a random state between the long fiber length carbon fibers increases the conductivity in the resulting molded product, further improving antistatic properties and electromagnetic wave shielding properties. The heat conductivity can be improved. The content of the short fiber length carbon fiber and the carbon compound is preferably in the range of 0.5% by mass to 20% by mass with respect to the polysiloxane-modified polylactic acid resin composition.

  As the expansive graphite, natural phosphorus pen graphite is treated with an inorganic acid and a strong oxidizing agent to form a graphite intercalation compound, and further, ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound It is preferable to use one that has been neutralized with, for example. The polysiloxane-modified polylactic acid resin composition of the present invention may contain other components as long as the function of the expandable graphite is not hindered.

  Specific examples of the commercially available expandable graphite include “GREP-EG” manufactured by Tosoh Corporation, “Moehen Z” series manufactured by Air Water, and the like. The expansive graphite may be subjected to a surface treatment. A sulfuric acid compound exists between the layers of the expandable graphite, and when the polylactic acid resin and other additives are melt-kneaded, the graphite is destroyed and the sulfuric acid compound is exposed on the surface. May cause degradation of the polylactic acid resin. As a result, for example, the mechanical properties of the polysiloxane-modified polylactic acid resin composition may be deteriorated. On the other hand, by subjecting the expandable graphite to surface treatment, exposure of the sulfate compound to the surface can be suppressed, and decomposition of the polylactic acid resin can be kept to a minimum.

  The surface treatment of the expandable graphite includes higher fatty acids such as stearic acid, oleic acid, linoleic acid, and linolenic acid, silane coupling agents such as epoxy silane, vinyl silane, methacryl silane, amino silane, alkoxy silane, and isocyanate silane, and titanate cups. Examples of the surface treatment include a ring agent, a sol-gel coating, a silicone polymer coating, and a resin coating.

  When the surface treatment is performed using a surface treatment agent, a general method such as a dry method, a wet method, a spray method, an integral blend method, or the like can be used. Specifically, while stirring the expandable graphite using a V blender or the like, a dry method in which the surface treatment agent is sprayed with dry air or nitrogen gas and treated, and the expandable graphite is dispersed in water to form a slurry state Then, a wet method in which a surface treatment agent is added and treated, a spray method in which the expansive graphite is heated in a high-temperature furnace and then the surface treatment agent is sprayed, the expansive graphite, and other resins. An integral blend method in which the material and the surface treatment agent are simultaneously charged into an extruder and processed can be used.

  As the surface treatment agent used in the dry method, wet method, and spray method, the surface treatment agent may be used as it is, or the surface treatment agent is diluted with an organic solvent (or water) to obtain a solution. May be used as

  As the amount of the expandable graphite, it is preferable to mix the expandable graphite in a range of 1% by mass to 50% by mass with respect to the polysiloxane-modified polylactic acid resin composition, and 5% by mass to 30% by mass. It is more preferable to mix in the range of%. If the compounding amount of the expandable graphite is 1% by mass or more, a sufficient flame retardancy imparting effect can be obtained. When the compounding amount of the expandable graphite is 50% by mass or less, it is possible to prevent deterioration of mechanical properties.

The polysiloxane-modified polylactic acid resin composition of the present invention may further contain a flame retardant. As the flame retardant, known ones can be used, but phosphorus flame retardants are preferable, and phosphazene derivatives and aromatic condensed phosphates are more preferable because they have an excellent flame retardant effect. Examples of the phosphazene derivative include cyclic cyclophosphazene compounds represented by the following formula.

n represents an integer of 3 or more, preferably in the range of 3 to 25, and more preferably in the range of 3 to 5. If n is 3, a 6-membered ring is formed by P (phosphorus element) and N (nitrogen element). If n is 4, an 8-membered ring is formed by P and N. The same applies when n is 5 or more. R ₁₉ and R ₂₀ each represent an organic group, for example, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted naphthoxy group (for example, β-naphthoxy group).

  Examples of the phosphazene derivative include a cyclophosphazene compound having a phenoxy group, a cyclophosphazene compound having a cyanophenoxy group, a cyclophosphazene compound having an aminophenoxy group, and a cyclophosphazene compound having a substituted or unsubstituted naphthoxy group. . Among these cyclophosphazene compounds, cyclotriphosphazene, cyclotetraphosphazene or cyclopentaphosphazene having a substituted or unsubstituted phenoxy group or a substituted or unsubstituted naphthoxy group is preferable, and a cyclohexane having a substituted or unsubstituted phenoxy group is preferable. Triphosphazene is particularly preferred. Specific examples include hexaphenoxycyclotriphosphazene (the phenoxy group may have a substituent). The cyclophosphazene compound preferably does not have a phenolic hydroxyl group because it easily forms a quinone structure that causes coloration by oxidation. The said phosphazene derivative may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aromatic condensed phosphate include resorcinol bisdiphenyl phosphate, bisphenol A, bisdiphenyl phosphate, resorcinol-bis-2,6-xylenyl phosphate, resorcinol-bis-2,6-bisdiphenyl phosphate, and biphenol- Bisphenyl phosphate, 4,4′-bis (diphenylphosphoryl) -1,1′-biphenyl and the like can be mentioned.

  The content of the flame retardant is preferably determined while confirming the effect. From the viewpoint of flame retardancy, bending fracture strain, impact resistance, heat resistance, and bleed resistance, polysiloxane-modified polylactic acid series The range of 0.5 mass%-20 mass% is preferable with respect to a resin composition, and the range of 1 mass%-15 mass% is more preferable.

  The polysiloxane-modified polylactic acid resin composition of the present invention may further contain a metal hydrate. In the metal hydrate, the content of the alkali metal substance in the metal hydrate is preferably 0.2% by mass or less from the viewpoint of suppressing hydrolysis of the polylactic acid resin. The alkali metal-based substance refers to an alkali metal such as lithium, sodium or potassium, or an oxide or chloride of an alkaline earth metal such as beryllium, magnesium, calcium, strontium or barium. The content of the alkali metal material can be measured by, for example, atomic absorption spectrometry, ICP emission spectroscopic analysis, or the like.

  Examples of the metal hydrate include aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, hydrated gypsum, calcium hydroxide, zinc borate, barium metaborate, borax, kaolin clay, and calcium carbonate. Aluminum hydroxide, magnesium hydroxide, and calcium hydroxide are preferable, and aluminum hydroxide is more preferable.

  Further, the metal hydrate is preferably made of a granular material having an average particle diameter of 10 nm or less, and more preferably made of a granular material having an average particle diameter of 0.1 μm to 5 μm. The average particle diameter of the metal hydrate can be determined by measuring the volume-based median diameter by a diffraction / scattering method, for example. Examples of commercially available devices that can measure the average particle size include a laser diffraction / light scattering particle size measuring device LS230 manufactured by Coulter, Inc.

  The metal hydrate may be subjected to a surface treatment with a silane coupling agent. The method for obtaining the metal hydrate surface-treated with the silane coupling agent is not particularly limited. For example, a solution obtained by dissolving the silane coupling agent in a solvent such as acetone, ethyl acetate, toluene, Examples thereof include a method of spraying or coating the surface of a metal hydrate having a substance content of 0.2% by mass or less and drying to remove the solvent.

  The polysiloxane-modified polylactic acid resin composition of the present invention preferably further contains a fluorine-containing polymer that forms a fiber structure (fibril structure) in the polysiloxane-modified polylactic acid resin composition. By blending the fluorine-containing polymer, it becomes possible to prevent a drip phenomenon during combustion.

  Examples of the fluorine-containing polymer include polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, a tetrafluoroethylene / hexafluoropropylene copolymer), and a partially fluorinated polymer. In addition, as the fluorine-containing polymer, various powders such as fine powder fluoropolymer, fluoropolymer aqueous disperser, powdery fluoropolymer / acrylonitrile / styrene copolymer mixture, powdery fluoropolymer / polymethyl methacrylate mixture, etc. Forms of fluoropolymers can also be used.

  The lower limit of the amount of the fluorine-containing polymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, relative to the polysiloxane-modified polylactic acid resin composition. In addition, the upper limit of the amount of the fluorine-containing polymer is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.8% with respect to the polysiloxane-modified polylactic acid resin composition. It is below mass%. When the blending amount of the fluorine-containing polymer is 0.05% by mass or more, the effect of preventing dripping during combustion can be stably obtained. When the blending amount of the fluoropolymer is 0.1% by mass or more, the flame retardancy of the polysiloxane-modified polylactic acid resin composition is further improved. When the blending amount of the fluorine-containing polymer is 5% by mass or less, it is easy to disperse in the resin, so that it can be easily mixed with the polysiloxane-modified polylactic acid resin composition and has a flame retardancy. Stable production of goods is possible. When the blending amount of the fluoropolymer is 1% by mass or less, flame retardancy is further improved. When the blending amount of the fluoropolymer is 0.8% by mass or less, the flame retardancy of the polysiloxane-modified polylactic acid resin composition is further improved.

  The polysiloxane-modified polylactic acid-based resin composition of the present invention has various crystal nucleating agents, plasticizers, heat stabilizers, antioxidants, colorants, fluorescent whitening agents, fillers, as long as the function is not hindered. It may contain additives such as mold release agents, softeners, antistatic agents, impact modifiers, endothermic agents such as metal hydroxides and borates, nitrogen compounds such as melamines, halogen flame retardants, and the like.

  When the polysiloxane-modified polylactic acid resin composition of the present invention contains a crystalline resin, a crystal nucleating agent is added in order to further promote crystallization of an amorphous component having a low flow start temperature in molding of a molded product. It is preferable to use it. The crystal nucleating agent itself becomes a crystal nucleus during molding of a molded product, and acts to arrange resin constituent molecules in a regular three-dimensional structure. Strength and heat resistance can be improved. Furthermore, the crystal nucleating agent promotes crystallization of the amorphous component, so that deformation of the molded product is suppressed even when the mold temperature during molding is high, and mold release after molding is easy. To. The same effect can be obtained even when the mold temperature is higher than the glass transition temperature (Tg) of the resin.

Examples of the crystal nucleating agent include inorganic crystal nucleating agents and organic crystal nucleating agents. Examples of the inorganic crystal nucleating agent include talc, calcium carbonate, mica, boron nitride, synthetic silicic acid, silicate, silica, kaolin, carbon black, zinc white, montmorillonite, clay mineral, basic magnesium carbonate, and quartz powder. Glass fiber, glass powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, boron nitride and the like can be used. Examples of the organic crystal nucleating agent include:
(1) Organic carboxylic acids: octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, montanic acid, melicic acid, benzoic acid, p-tert- Butyl benzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, isophthalic acid monomethyl ester, rosin acid, 12-hydroxystearic acid, cholic acid, etc.
(2) Organic carboxylic acid alkali metal salt and organic carboxylic acid alkaline earth metal salt: alkali metal salt and alkaline earth metal salt of organic carboxylic acid,
(3) Polymer organic compound having carboxyl group metal salt: carboxyl group-containing polyethylene obtained by oxidation of polyethylene, carboxyl group-containing polypropylene obtained by oxidation of polypropylene, olefins such as ethylene, propylene, butene-1 and acrylic Metal salts such as copolymers of acid or methacrylic acid, copolymers of styrene and acrylic acid or methacrylic acid, copolymers of olefins and maleic anhydride, copolymers of styrene and maleic anhydride, etc. ,
(4) Aliphatic carboxylic acid amide: oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, N-oleyl palmitoamide, N-stearyl erucic acid amide, N, N′-ethylenebis (stearoamide), N, N'-methylenebis (stearoamide), methylol stearoamide, ethylene bisoleic acid amide, ethylene bisbehenic acid amide, ethylene bisstearic acid amide, ethylene bislauric acid amide, hexamethylene bis oleic acid amide, hexamethylene bisstearic acid Amide, Butylenebisstearic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N′-distearyl sebacic acid amide, m-xyl Nbis stearic acid amide, N, N′-distearylisophthalic acid amide, N, N′-distearyl terephthalic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-stearyl erucic acid amide, N -Oleyl stearamide, N-stearyl stearamide, N-butyl-N'-stearyl urea, N-propyl-N'-stearyl urea, N-allyl-N'-stearyl urea, N-phenyl-N'- Stearyl urea, N-stearyl-N'-stearyl urea, dimethylol oil amide, dimethyl lauric acid amide, dimethyl stearic acid amide, N, N'-cyclohexane bis (stearoamide), N-laureululu L-glutamic acid-α, γ-n -Butyramide, etc.
(5) High molecular organic compound: carbon such as 3,3-dimethylbutene-1,3-methylbutene-1,3-methylpentene-1,3-methylhexene-1,3,5,5-trimethylhexene-1 A 5-position branched α-olefin having a number of 5 or more, and a polymer of vinylcycloalkane such as vinylcyclopentane, vinylcyclohexane, vinylnorbornane, polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polyglycolic acid, cellulose, cellulose ester, Cellulose ether, polyester, polycarbonate, etc.
(6) Organic compounds of phosphoric acid or phosphorous acid and their metal salts: diphenyl phosphate, diphenyl phosphite, bis (4-tert-butylphenyl) sodium phosphate, methylene phosphate (2,4-tert- Butylphenyl) sodium, etc.
(7) sorbitol derivatives such as bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol,
(8) Cholesterol derivatives such as cholesteryl stearate and cholesteryloxy system aramid,
(9) Thioglycolic anhydride, p-toluenesulfonic acid, p-toluenesulfonic acid amide and their metal salts, etc.
(10) Phenylphosphonic acid and its metal salt can be mentioned.

  Among these, a crystal nucleating agent made of a neutral substance that does not promote polyester hydrolysis is preferable because the polysiloxane-modified polylactic acid-based resin composition can be prevented from undergoing hydrolysis and the molecular weight can be reduced. In addition, in order to suppress the reduction in molecular weight due to the transesterification reaction of the polysiloxane-modified polylactic acid-based resin composition, an ester or amide compound that is a derivative thereof is preferable to a crystal nucleating agent having a carboxy group, An ester or ether compound which is a derivative thereof is preferred to a crystal nucleating agent having a hydroxy group.

  The inorganic crystal nucleating agent is compatible or finely dispersed with a resin in a high-temperature molten state in injection molding or the like, and precipitates or phase-separates in a molding cooling step in a mold to act as a crystal nucleus, talc, etc. The layered compound is preferred. As the crystal nucleating agent, an inorganic crystal nucleating agent and an organic crystal nucleating agent may be used in combination, or a plurality of types may be used in combination. The content of the crystal nucleating agent is preferably in the range of 0.1% by mass to 20% by mass in the composition.

  Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, vitamin E, and the like. These are preferably used in the range of 0.5% by mass or less with respect to the polylactic acid resin.

  Examples of the filler include glass beads, glass flakes, talc powder, clay powder, mica, wollastonite powder, and silica powder.

  As the impact resistance improving material, a soft component can be used. Examples of the soft component include a block in which a polymer block (copolymer) such as a polyester segment, a polyether segment, and a polyhydroxycarboxylic acid segment, a polylactic acid segment, an aromatic polyester segment, and a polyalkylene ether segment are bonded to each other. Copolymer, block copolymer consisting of polylactic acid segment and polycaprolactone segment, polymer based on unsaturated carboxylic acid alkyl ester unit, polybutylene succinate, polyethylene succinate, polycabrolactone, polyethylene adipate, Aliphatic polyesters such as polypropylene adipate, polybutylene adipate, polyhexene adipate, polybutylene succinate adipate, polyethylene glycol and its Steal, polyglycerin acetate, epoxidized soybean oil, epoxidized linseed oil, epoxidized linseed oil fatty acid butyl, adipic acid aliphatic polyester, acetyl citrate tributyl, acetyl ricinoleic acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, Examples thereof include plasticizers such as adipic acid dialkyl ester and alkylphthalyl alkyl glycolate.

  The polysiloxane-modified polylactic acid-based resin composition of the present invention further contains other thermoplastic resins, such as polypropylene, polystyrene, ABS, nylon, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and alloys thereof as necessary. May be included. It is preferable to use a thermosetting resin having crystallinity, for example, polypropylene, nylon, polyethylene terephthalate, polybutylene terephthalate, an alloy with these polylactic acid resins, and the like.

  The polysiloxane-modified polylactic acid resin composition of the present invention further comprises a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, an epoxy resin, a silicone resin, and a cyanate resin. Thermosetting resin, isocyanate resin, furan resin, ketone resin, xylene resin, thermosetting polyimide, thermosetting polyamide, styrylpyridine resin, nitrile terminal resin, addition curing type quinoxaline, addition curing type polyquinoxaline resin, etc. A thermosetting resin using a plant material such as a curable resin or lignin, hemicellulose, or cellulose may be included. When using the said thermosetting resin, it is preferable to use the hardening | curing agent and hardening accelerator which are required for hardening reaction.

  The polysiloxane-modified polylactic acid resin composition of the present invention can be produced, for example, as follows. That is, first, the polylactic acid resin, the carbon fiber, the expandable graphite, and other additive components as necessary are mixed and stirred. For this mixing and stirring, an apparatus similar to an apparatus for applying a shearing force in the production of a polylactic acid resin described later can be used. When using copper-plated aramid fiber or stainless steel fiber as a thermal conductivity imparting agent instead of carbon fiber or in combination with carbon fiber, compound pellets containing mastered copper-plated aramid fiber or stainless fiber (master) Batched pellets) can be used. If the carbon fiber, the pellet, and the expandable graphite are supplied from a side feed or the like, the carbon fiber, the copper-plated aramid fiber, the stainless fiber, or the like and the expandable graphite can be prevented from being broken or pulverized. Moreover, when using the said pellet, the molded object of the polysiloxane modified polylactic acid-type resin composition of this invention is obtained by dry blending the said pellet and the pellet of the said polylactic acid-type resin, and carrying out injection molding. Can do. Breaking or crushing the copper-plated aramid fiber, the stainless steel fiber, or the like can be significantly suppressed by not passing through the shearing force due to the mixing and stirring step.

  The polylactic acid-based resin is prepared by, for example, blending the amino group-containing polysiloxane compound prepared in advance with the polylactic acid-based compound in a ratio such that the amino group has a predetermined ratio, and shearing force in a molten state. It can be obtained by mixing and stirring while adding. In addition, when the segment of the amino group-containing polysiloxane compound is composed of a reaction product of the amino group-containing polysiloxane compound and the epoxy group-containing polysiloxane compound, the amino group-containing polysiloxane compound, the epoxy The group-containing polysiloxane compound and the polylactic acid-based compound may be simultaneously blended and mixed and stirred, but the reaction of the amino group-containing polysiloxane compound and the polylactic acid-based compound is performed in advance, and then the epoxy It is preferable to carry out the reaction of the group-containing polysiloxane compound. In order to give a shearing force to the melted polylactic acid compound and amino group-containing polysiloxane compound, for example, a roll, an extruder, a kneader, a batch kneader with a reflux device, or the like can be used. As the extruder, it is preferable to use a single-shaft or multi-shaft vented unit because it is easy to supply raw materials and take out products. The temperature at the time of shearing is preferably not less than the melt flow temperature of the raw polylactic acid compound, preferably 10 ° C. or more higher than the melt flow temperature and not more than the decomposition temperature. For example, the melt shearing time is preferably in the range of 0.1 to 30 minutes, and more preferably in the range of 0.5 to 10 minutes. When the melt shear time is 0.1 minutes or longer, the reaction between the polylactic acid compound and the amino group-containing polysiloxane compound is sufficiently performed. When the melt shear time is 30 minutes or less, decomposition of the resulting polylactic acid resin can be suppressed.

  The polylactic acid-based compound can be produced by a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method. In these methods, as a method for adjusting the melt flow rate of the polylactic acid compound to a predetermined range, when the melt flow rate is excessive, a small amount of chain extender, for example, diisocyanate compound, epoxy compound, acid A method of increasing the molecular weight of the resin using an anhydride or the like can be used. When the melt flow rate is too low, a method of mixing with a biodegradable polyester resin having a high melt flow rate or a low molecular weight compound can be used.

Examples of the polylactic acid resin include those represented by the following formulas (3) to (5), the following formula (8), the following formula (11), and the following formulas (13) to (18). it can.
In the above formulas (3) to (5), (8), (11) and (13) to (18),
R ₁ , R ₂ , R _{4 to} R ₈ , R _{4 ′} R _{10 to} R ₁₄ and R _{10 ′} are each an alkyl group having 18 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, — (the alpha, 1 to 8 _{integer) (CH 2) α -NH-} C 6 H 5 represents, they may be all or part by a halogen atom is _substituted, R _{1, R} 2, R _{4 to} R ₈ , R _{4 ′} R _{10 to} R ₁₄ and R _{10 ′} may be the same or different,
R ₃ , R ₉ , R ₁₅ and R ₁₆ each represent a divalent organic group, and R ₃ , R ₉ , R ₁₅ and R ₁₆ may be the same or different,
R ₁₇ represents an alkyl group having 18 or less carbon atoms,
d ′, e ′, h ′, i ′, n ′ and b ′ each represent an integer of 0 or more,
f, g, j, k, a and c each represent an integer of 1 or more,
X and W each represent a group represented by the following formula (6).
In the formula (6),
R ₁₇ represents an alkyl group having 18 or less carbon atoms,
b ′ represents an integer of 0 or more;
a and c represent an integer of 1 or more.

  In the polylactic acid-based resin represented by these formulas, the repeating units that are repeated by the number of repeating units a, b ′, d ′, e ′, f, g, h ′, i ′, j, and k are the same type of repeating units. The units may be connected continuously or alternately. Moreover, as an alkyl group in the said Formula (6), a methyl group is especially preferable.

  The polysiloxane-modified polylactic acid resin composition of the present invention may include an unreacted epoxy group-containing polysiloxane compound or a reaction product of the amino group-containing polysiloxane compound and the epoxy group-containing polysiloxane compound. The polysiloxane-modified polylactic acid resin composition of the present invention has an affinity for the unreacted epoxy group-containing polysiloxane compound and the reaction product of the amino group-containing polysiloxane compound and the epoxy group-containing polysiloxane compound. Since it is high, the impact resistance and flexibility can be improved without bleeding of the polysiloxane compound in the molded product.

  According to this invention, the molded article shape | molded using the said polysiloxane modified polylactic acid-type resin composition can be obtained. As the molding method of the molded product, for example, injection molding, injection / compression molding, extrusion molding, and mold molding can be used. It is preferable to promote crystallization during the manufacturing process or after molding because a molded article having excellent impact resistance and mechanical strength can be obtained. Examples of the method for promoting crystallization include a method using the crystal nucleating agent in the above range.

  Such a molded article has high flame retardancy and thermal conductivity, excellent impact resistance, excellent mechanical strength, and suppressed deterioration due to bleeding, such as various types of electricity, electronics, automobiles, etc. Suitable for parts.

  Next, examples of the present invention will be described together with comparative examples and reference examples. The present invention is not limited or restricted by the following examples and comparative examples. The detail of each raw material used for the Example and comparative example of this invention is as follows.

1. Polylactic acid compound (PLA)
(PLA-1): Terramac TE-4000N (melting point: 170 ° C.) manufactured by Unitika Ltd.
(PLA-2): Terramac TP-4000 (melting point: 170 ° C.) manufactured by Unitika Ltd.

2. Amino group-containing polysiloxane compound (C)
The side chain diamino type polysiloxane compound (C1-4) used as the amino group-containing polysiloxane compound (C) is shown in Table 1. The amino group-containing polysiloxane compound can be produced, for example, according to the description of Silicone Handbook (published by Nikkan Kogyo Shimbun, p. 165). For example, siloxane oligomer obtained by hydrolysis of aminoalkylmethyldimethoxysilane and cyclic Synthesized using siloxane and basic catalyst.

3. Epoxy group-containing polysiloxane compound (D)
Table 2 shows the both-end epoxy type polysiloxane compound (D1) used as the epoxy group-containing polysiloxane compound (D). The epoxy group-containing polysiloxane compound can be produced, for example, according to the description in Silicone Handbook (published by Nikkan Kogyo Shimbun, p. 164). For example, dimethylpolysiloxane having an Si—H group and allylglycidyl ether, etc. A saturated epoxy compound is subjected to an addition reaction under a platinum catalyst.

4). Organic crystal nucleating agent (E)
The following two were used as the organic crystal nucleating agent (E).
E-1: ITOHWAX J-530 (N.N′-ethylenebis-12hydroxystearylamide) manufactured by Ito Oil Co., Ltd.
E-2: Eco Promote (Zinc Phenylphosphonate) manufactured by Nissan Chemical Industries, Ltd.

5. Carbon fiber (F)
As the carbon fiber (F), pitch-based carbon fiber having anisotropy of 6 mm in fiber length was used.
Carbon fiber (F): DIALEAD K6371T manufactured by Mitsubishi Plastics Co., Ltd.
The physical properties are shown in Table 3.

6). Expandable graphite (G)
The following two were used as the expandable graphite (G).
G-1: “GREP-EG” manufactured by Tosoh Corporation
(Granularity 48 mesh ≧ 65% (300 μm opening))
G-2: “Moehen Z” MZ-600 manufactured by Air Water
(Granularity 80 mesh ≧ 80% (180 μm opening))

7). Phosphorus flame retardant (H)
The following was used as the phosphorus flame retardant (H).
H: Cyclic phenoxyphosphazene (SPS-100) manufactured by Otsuka Chemical Co., Ltd.

8). Metal hydrate (I)
As the metal hydrate (I), the following was used.
I-1: 1% isocyanate silane coupling agent manufactured by Showa Denko KK (HP-350-ICN *, average particle size: 3.1 μm, composition: Al (OH) ₃ (99.94% ), SiO ₂ (0.01%), Fe ₂ O ₃ (0.01%), Na ₂ O (0.04%, alkali metal based material))
I-2: Aluminum hydroxide (HP-350, average particle size: 3.2 μm, composition: Al (OH) ₃ (99.95%), SiO ₂ (0.01%), manufactured by Showa Denko KK Fe ₂ O ₃ (0.01%), Na ₂ O (0.03%, alkali metal substances))

9. Fluoropolymer (J)
The following was used as the fluorine-containing polymer (J).
J: Polytetrafluoroethylene (Polyfluorocarbon FA-500) manufactured by Daikin

10. Crystal nucleating agent (K)
The following were used as the crystal nucleating agent (K).
K: Polydiisopropylphenylcarbodiimide (Stavaxol P) manufactured by Rhein Chemie

11. Plasticizer (M)
The following was used as the plasticizer (M).
M: Adipic acid ester (DAIFACTY-101) manufactured by Daihachi Chemical Industry Co., Ltd.

12 Copper-plated aramid fiber (Cu)
The following was used as the copper-plated aramid fiber (Cu).
Cu: Copper-plated aramid fiber masterbatch (EMI-AGR26156) manufactured by Toyo Ink Manufacturing Co., Ltd.

[Examples 1 to 41, Comparative Examples 1 to 15 and Reference Examples]
Tables 5 to 5 show polylactic acid compounds and, if necessary, organic crystal nucleating agents (E), phosphorus flame retardants (H), metal hydrates (I), and fluorine-containing polymers (J). A mixture obtained by dry blending with the composition shown in FIG. 13 is supplied from a hopper port of a continuous kneading extruder (Berstorf ZE40A × 40D, L / D = 40, screw diameter φ40) set to a cylinder temperature of 190 ° C., and The amino group-containing polysiloxane compound (C1-4) and the epoxy group-containing polysiloxane compound (D1) are blended separately as shown in Tables 5 to 13, and are charged separately from the vent port. Further, the carbon fiber (F), expandable Graphite (G) and copper-plated aramid fiber master batch (Cu) were supplied from the side feed port so that the total supply amount per hour was 15 to 20 kg. The screw was rotated at 150 rpm, mixed and stirred under melt shearing, then extruded into a strand from the die port of the extruder, cooled in water, then cut into pellets, and a polysiloxane-modified polylactic acid resin composition Pellets were obtained.

  The obtained pellets were dried at 100 ° C. for 5 hours, and then a test piece (125 × 13) using an injection molding machine (EC20P-0.4A manufactured by Toshiba Machine, molding temperature: 190 ° C., mold temperature: 25 ° C.). × 1.6 mm or 3.2 mm) was molded, and flame retardancy evaluation, Izod impact strength and bending strain evaluation, and thermal conductivity evaluation were performed by the following methods. The results are shown in Tables 5 to 13 and FIG.

[Example 42]
Regarding the components excluding the copper-plated aramid fiber master batch (Cu) among the formulations shown in Table 14, pellets obtained in the same manner as in the method for producing pellets of the polysiloxane-modified polylactic acid resin composition were obtained at 100 ° C. After drying for a while, dry blended with copper-plated aramid fiber masterbatch (Cu) and tested using an injection molding machine (EC20P-0.4A manufactured by Toshiba Machine, molding temperature: 190 ° C, mold temperature: 25 ° C) A piece (125 × 13 × 1.6 mm or 3.2 mm) was molded, and flame retardancy evaluation, Izod impact strength and bending strain evaluation, and thermal conductivity evaluation were performed by the following methods. The results are shown in Table 14.

(Flame retardance evaluation)
The flame retardancy evaluation was performed by leaving a test piece (125 mm × 13 mm × 1.6 mm or 3.2 mm) for flame retardancy evaluation obtained by injection molding in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50% for 48 hours. In accordance with UL94 test (flammability test of plastic materials for equipment parts) established by Underwriters Laboratories. UL94V is a method for evaluating flame retardancy from the afterflame time and drip properties after a burner flame is indirectly fired for 10 seconds on a test piece of a predetermined size held vertically, as shown in Table 4 below. Divided into classes.

  In addition, when taking combustion forms other than the said classification | category, it classified as notV-2. When the evaluation results are arranged in order of good flame retardancy, V-0, V-1, and (V-2 or notV-2) are obtained.

  The after-flame time is the length of time that the test piece continues to burn with flame after the ignition source is moved away, t1 is the after-flame time after completion of the first flame contact, and t2 is The after-flame time after the end of the second flame contact, t3, is the afterglow (flameless combustion) time after the end of the second flame contact. The second flame contact is performed by indirect flame for 10 seconds with a burner immediately after the first flame contact, after the flame has disappeared. Further, the ignition of cotton by the drip is determined by whether or not the labeling cotton that is about 300 mm below the lower end of the test piece is ignited by a drip from the test piece. When the afterflame time could not be measured because the sample piece was burned out, it was indicated as “−” in the table.

(Evaluation of Izod impact strength and bending strain)
The test piece was allowed to stand in a thermostatic chamber at 110 ° C. for 2 hours to crystallize, and then returned to room temperature to evaluate Izod impact strength and bending characteristics. The Izod impact strength was measured according to JIS K7110 by notching the test piece and measuring the impact strength. The bending properties were evaluated using a universal testing machine (Instron 5567) based on ASTM D790.

(Thermal conductivity evaluation)
A test piece (125 mm × 13 mm × 1.6 mm) was fixed to a support base, and steady heat was applied to a part of the test piece with a rubber heater previously heated to 80 ° C. A state in which heat is diffused from the contact portion with the rubber heater to the entire test piece is measured by an infrared thermotracer (thermo scanner TS5304 manufactured by NEC Sanei), and thermal conductivity (surface) is measured by thermography analysis shown in FIG. (Inner heat diffusivity) was evaluated. In FIG. 1, the left is an actual thermographic analysis image, and the right is a schematic diagram thereof. The thermal conductivity a of the test piece was evaluated according to the following criteria as a ratio of the stainless steel plate having the same shape as the test piece to the thermal conductivity b, a / b. The ratio a / b is obtained by adjusting the scale so that a gradation of color (temperature) appears in the thermographic analysis, and comparing the heights of portions showing the same color (temperature). In the example shown in FIG. 1, the heights of the boundary between orange and yellow are compared.
◎: a / b is 0.9 or more ○: a / b is 0.5 or more and less than 0.9 Δ: a / b is 0.3 or more and less than 0.5 ×: a / b is less than 0.3

  As shown in Table 5 and Table 6, the polysiloxane-modified polylactic acid resin compositions of Examples 1 to 6 have higher flame retardancy and heat than the resin compositions of Comparative Examples 1 to 6 and Reference Example 1. It was found to have good impact strength and breaking bending strain while having conductivity.

  As shown in Table 7, the polysiloxane-modified polylactic acid-based resin compositions of Examples 7 to 12 are highly flame retardant compared to the polylactic acid-based resin compositions of Comparative Examples 7 to 9 that are not polysiloxane-modified. It has been found that it has good impact strength and breaking bending strain while having heat resistance and thermal conductivity.

  As shown in the said Table 8, it turns out that the polysiloxane modified polylactic acid-type resin composition of Examples 13-15 is excellent in a flame retardance. When using expansive graphite (G-2) with a fine particle size, combined with metal hydrate (I), in addition to high flame resistance and thermal conductivity, good impact strength and fracture bending It was found that distortion was obtained.

  From Examples 16 to 18 in Table 9 above, it can be seen that by using the plasticizer (M) in combination, the impact strength and fracture bending strain are further improved while having high flame retardancy and thermal conductivity. . In addition, the polysiloxane-modified polylactic acid resin composition of Example 18 had excellent flame conductivity and good heat conduction compared to the polylactic acid resin composition of Comparative Example 11 that was not modified with polysiloxane. It can be seen that the material has the property, impact strength and breaking bending strain. Furthermore, the polysiloxane-modified polylactic acid resin compositions of Examples 18 to 19 have excellent flame retardancy compared to the polylactic acid resin composition of Comparative Example 12 that does not contain carbon fiber (F). However, it can be seen that it has good thermal conductivity, impact strength and breaking bending strain. And when Example 18 and Example 20 are compared, when using expandable graphite (G-2) with a fine particle size, it is more difficult to use it together with the phosphorus-based flame retardant (H). It was found that flammability was obtained, and excellent thermal conductivity, good impact strength and breaking bending strain were obtained.

  As shown in Table 10, the polysiloxane-modified polylactic acid resin compositions of Examples 21 to 22, 23 to 26 have good impact strength and breaking bending strain while having high flame retardancy and thermal conductivity. Have. From these results, it was found that by using the plasticizer (M) in combination, the impact strength and the bending bending strain were further improved while having high flame retardancy and thermal conductivity. In addition, the polysiloxane-modified polylactic acid resin compositions of Example 23 and Example 26 were superior in flame retardancy compared to the polylactic acid resin compositions of Comparative Examples 13 and 14 that were not modified with polysiloxane. It can be seen that it has good thermal conductivity, impact strength and fracture bending strain.

  As shown in Table 11, the polysiloxane-modified polylactic acid-based resin compositions of Examples 27 to 28 have good impact strength and breaking bending strain while having high flame retardancy and thermal conductivity. From these results, it was found that by using the plasticizer (M) in combination, the impact strength and the bending bending strain were further improved while having high flame retardancy and thermal conductivity.

  As shown in Table 12, the polysiloxane-modified polylactic acid resin compositions of Examples 29 to 35 have good impact strength and breaking bending strain while having high flame retardancy and thermal conductivity.

  As shown in Table 13, the polysiloxane-modified polylactic acid-based resin compositions of Examples 36 to 41 have high impact resistance and breaking bending strain while having high flame retardancy and thermal conductivity. On the other hand, it can be seen that the high flame retardancy cannot be obtained with the polylactic acid resin composition of Comparative Example 15 that does not use expandable graphite (G-2).

  As shown in Table 14, the polysiloxane-modified polylactic acid resin composition of Example 42 has high impact resistance and breaking bending strain while having high flame retardancy and thermal conductivity.

  As described above, the polysiloxane-modified polylactic acid resin composition of the present invention has high flame retardancy and thermal conductivity, and further has excellent impact resistance and flexibility. The use of the polysiloxane-modified polylactic acid resin composition of the present invention is not particularly limited, and can be widely applied to, for example, home appliances, OA equipment housings, automobile parts, and the like.

  A part or all of the above embodiment can be described as in the following supplementary notes, but is not limited to the following.

(Appendix 1) A polylactic acid resin, a thermal conductivity imparting agent, and expandable graphite.
The polylactic acid resin is
A segment of polylactic acid compound,
A segment of an amino group-containing polysiloxane compound having an amino group in the side chain,
The content of the amino group with respect to the amino group-containing polysiloxane compound is in the range of 0.01% by mass to 2.5% by mass,
The polysiloxane modified polylactic acid resin composition, wherein the compounding amount of the amino group with respect to the polylactic acid compound is in the range of 3 ppm by mass to 300 ppm by mass.

(Supplementary note 2) The supplementary note 1, wherein the amino group-containing polysiloxane compound includes at least one of a compound represented by the formula (1) and a compound represented by the formula (2). A polysiloxane-modified polylactic acid resin composition.

(Appendix 3) The segment of the amino group-containing polysiloxane compound includes a segment composed of a reaction product of the amino group-containing polysiloxane compound and an epoxy group-containing polysiloxane compound having an epoxy group. The polysiloxane-modified polylactic acid resin composition according to Supplementary Note 1 or Supplementary Note 2.

(Supplementary Note 4) The epoxy group-containing polysiloxane compound is at least selected from the group consisting of compounds represented by the formula (12), the formula (19), the formula (20), and the formula (21), respectively. The polysiloxane-modified polylactic acid-based resin according to supplementary note 3, wherein the epoxy group content of the compound represented by the formulas (19) and (21) is less than 2% by mass, including one kind of compound Composition.

(Additional remark 5) The said polylactic acid-type resin consists of a compound respectively represented by said Formula (3)-(5), said Formula (8), said Formula (11), and said Formula (13)-(18). 5. The polysiloxane-modified polylactic acid resin composition according to any one of appendices 1 to 4, comprising at least one compound selected from the group.

(Supplementary note 6) The polysiloxane-modified polylactic acid-based resin composition according to supplementary note 5, wherein in the formula (6), R ₁₇ is a methyl group.

(Additional remark 7) Furthermore, content of the said phosphorus flame retardant is 0.5 mass%-20 mass% with respect to the said polysiloxane modified polylactic acid-type resin composition including a phosphorus flame retardant. The polysiloxane-modified polylactic acid resin composition according to any one of appendices 1 to 6, wherein the composition is a range.

(Additional remark 8) Furthermore, the content of the alkali metal substance includes a metal hydrate having a content of 0.2% by mass or less, and the content of the metal hydrate is in the polysiloxane-modified polylactic acid resin composition. On the other hand, the polysiloxane-modified polylactic acid resin composition according to any one of appendices 1 to 7, which is in a range of 0.05% by mass to 40% by mass.

(Additional remark 9) Furthermore, it contains fluorine-containing polymer, and content of the said fluorine-containing polymer is the range of 0.05 mass%-5 mass% with respect to the said polysiloxane modified polylactic acid-type resin composition, It is characterized by the above-mentioned. The polysiloxane-modified polylactic acid resin composition according to any one of appendices 1 to 8.

(Additional remark 10) Furthermore, it contains a plasticizer, Content of the said plasticizer is the range of 0.05 mass%-20 mass% with respect to the said polysiloxane modified polylactic acid-type resin composition, It is characterized by the above-mentioned. The polysiloxane-modified polylactic acid resin composition according to any one of appendices 1 to 9.

(Supplementary note 11) The polysiloxane-modified polylactic acid resin composition according to any one of supplementary notes 1 to 10, wherein the thermal conductivity imparting agent is at least one of carbon fiber and copper-plated aramid fiber.

(Additional remark 12) The molded product characterized by shape | molding with the polysiloxane modified polylactic acid-type resin composition in any one of Additional remarks 1-11.

(Supplementary note 13) The molded article according to Supplementary note 12, which is molded by at least one molding method selected from the group consisting of injection molding, injection / compression molding, extrusion molding and die molding.

(Supplementary note 14) A step of mixing and stirring an amino group-containing polysiloxane compound having an amino group in a side chain and a molten polylactic acid compound, and further mixing and stirring a thermal conductivity-imparting agent and expandable graphite is provided. And
The content of the amino group with respect to the amino group-containing polysiloxane compound is in the range of 0.01% by mass to 2.5% by mass,
The method for producing a polysiloxane-modified polylactic acid resin composition, wherein the compounding amount of the amino group with respect to the polylactic acid compound is in the range of 3 ppm by mass to 300 ppm by mass.

(Additional remark 15) The manufacturing method of the polysiloxane modified polylactic acid-type resin composition of Additional remark 14 which uses at least one of carbon fiber and a copper plating aramid fiber as said thermal conductivity imparting agent.

(Supplementary Note 16) A polysiloxane-modified polylactic acid resin composition produced by the production method according to Supplementary Note 14 or 15.

Claims (10)

Including a polylactic acid-based resin, a thermal conductivity imparting agent and expandable graphite,
The polylactic acid resin is
A segment of polylactic acid compound,
A segment of an amino group-containing polysiloxane compound having an amino group in the side chain,
The content of the amino group with respect to the amino group-containing polysiloxane compound is in the range of 0.01% by mass to 2.5% by mass,
The polysiloxane modified polylactic acid resin composition, wherein the compounding amount of the amino group with respect to the polylactic acid compound is in the range of 3 ppm by mass to 300 ppm by mass. The polysiloxane modification according to claim 1, wherein the amino group-containing polysiloxane compound contains at least one of a compound represented by the following formula (1) and a compound represented by the following formula (2). Polylactic acid resin composition.
In the above formulas (1) and (2),
R _{4 to} R ₈ , R _{4 ′} , R _{10 to} R ₁₄ and R _{10 ′} are each an alkyl group having 18 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, — (CH ₂ ) _α —NH—C ₆ H ₅ (α is an integer of 1 to 8), which may be wholly or partially substituted with a halogen atom, and R _{4 to} R ₈ , R _{4 ′} , R ₁₀ ~ R ₁₄ and R _{10 '} may be the same or different,
R ₉ , R ₁₅ and R ₁₆ each represent a divalent organic group, and R ₉ , R ₁₅ and R ₁₆ may be the same or different,
d ′ and h ′ each represent an integer of 0 or more;
e and i each represents an integer of 1 or more. The segment of the amino group-containing polysiloxane compound includes a segment composed of a reaction product of the amino group-containing polysiloxane compound and an epoxy group-containing polysiloxane compound having an epoxy group. 3. The polysiloxane-modified polylactic acid resin composition according to 2. The epoxy group-containing polysiloxane compound is at least one compound selected from the group consisting of compounds represented by the following formula (12), the following formula (19), the following formula (20), and the following formula (21). 4. The polysiloxane-modified polylactic acid resin composition according to claim 3, wherein the epoxy group content of the compounds represented by the formulas (19) and (21) is less than 2% by mass.
In the above formulas (12), (19), (20) and (21),
R ₁ , R ₂ and R _{18 to} R ₂₁ are each an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, — (CH ₂ ) _α -NH—C ₆ H ₅ ( α represents an integer of 1 to 8), which may be wholly or partially substituted with a halogen atom, and R ₁ , R ₂ , R _{18 to} R ₂₁ may be the same or different;
R ₃ represents a divalent organic group,
l ′ and n ′ each represents an integer of 0 or more,
m represents an integer of 1 or more. The polylactic acid resin is selected from the group consisting of compounds represented by the following formulas (3) to (5), the following formula (8), the following formula (11), and the following formulas (13) to (18). 5. The polysiloxane-modified polylactic acid-based resin composition according to claim 1, comprising at least one compound.
In the above formulas (3) to (5), (8), (11) and (13) to (18),
R ₁ , R ₂ , R _{4 to} R ₈ , R _{4 ′} R _{10 to} R ₁₄ and R _{10 ′} are each an alkyl group having 18 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, — (the alpha, 1 to 8 _{integer) (CH 2) α -NH-} C 6 H 5 represents, they may be all or part by a halogen atom is _substituted, R _{1, R} 2, R _{4 to} R ₈ , R _{4 ′} R _{10 to} R ₁₄ and R _{10 ′} may be the same or different,
R ₃ , R ₉ , R ₁₅ and R ₁₆ each represent a divalent organic group, and R ₃ , R ₉ , R ₁₅ and R ₁₆ may be the same or different,
R ₁₇ represents an alkyl group having 18 or less carbon atoms,
d ′, e ′, h ′, i ′, n ′ and b ′ each represent an integer of 0 or more,
f, g, j, k, a and c each represent an integer of 1 or more,
X and W each represent a group represented by the following formula (6).
In the formula (6),
R ₁₇ represents an alkyl group having 18 or less carbon atoms,
b ′ represents an integer of 0 or more;
a and c each represents an integer of 1 or more. In addition, it contains a phosphorus flame retardant,
The content of the phosphorus flame retardant is in the range of 0.5% by mass to 20% by mass with respect to the polysiloxane-modified polylactic acid resin composition. The polysiloxane modified polylactic acid resin composition according to claim 1. In addition, a metal hydrate having an alkali metal content of 0.2% by mass or less,
The content of the metal hydrate is in the range of 0.05% by mass to 40% by mass with respect to the polysiloxane-modified polylactic acid resin composition. The polysiloxane-modified polylactic acid resin composition described in the item. Furthermore, including a fluorine-containing polymer,
The content of the fluorine-containing polymer is in a range of 0.05% by mass to 5% by mass with respect to the polysiloxane-modified polylactic acid resin composition. A polysiloxane-modified polylactic acid resin composition described in 1. In addition, including a plasticizer,
The content of the plasticizer is in a range of 0.05% by mass to 20% by mass with respect to the polysiloxane-modified polylactic acid resin composition, according to any one of claims 1 to 8. The polysiloxane-modified polylactic acid resin composition described. Mixing and stirring an amino group-containing polysiloxane compound having an amino group in the side chain and a polylactic acid-based compound in a molten state, and further mixing and stirring a thermal conductivity-imparting agent and expandable graphite;
The content of the amino group with respect to the amino group-containing polysiloxane compound is in the range of 0.01% by mass to 2.5% by mass,
The method for producing a polysiloxane-modified polylactic acid resin composition, wherein the compounding amount of the amino group with respect to the polylactic acid compound is in the range of 3 ppm by mass to 300 ppm by mass.