WO2005075564A1

WO2005075564A1 - Resin composition and molded object obtained by molding the same

Info

Publication number: WO2005075564A1
Application number: PCT/JP2005/001671
Authority: WO
Inventors: Hiroo Kamikawa
Original assignee: Unitika Ltd.
Priority date: 2004-02-06
Filing date: 2005-02-04
Publication date: 2005-08-18
Also published as: JP5300173B2; JPWO2005075564A1

Abstract

A resin composition. The composition comprises 30 to 90% by mass crosslinked biodegradable polyester resin (A), 10 to 70% by mass polycarbonate resin (B), and 0 to 50% by mass acrylonitrile/butadiene/styrene copolymer resin (C), the sum of the resins (A) to (C) being 100% by mass.

Description

Specification

Resin composition and molded article obtained by molding the same

Technical field

The present invention relates to a resin composition and a molded product obtained by molding the same.

Background art

[0002] In recent years, biodegradable polyester resins such as polylactic acid have attracted attention from the viewpoint of environmental protection. Among the biodegradable resins, polylactic acid is one of the resins with high heat resistance, and can be mass-produced. Furthermore, polylactic acid can be produced using plants such as corn and sweet potato as raw materials, and can contribute to saving of dead resources such as petroleum.

[0003] However, even among polylactic acids having high heat resistance among biodegradable resins, polypropylene resin, acrylonitrile Z-butadiene Z-styrene copolymer resin (hereinafter abbreviated as "ABS resin"). Heat resistance is not always sufficient as compared with general-purpose resins such as polyester resin. Deterioration is remarkable in a high-temperature and high-humidity environment where mechanical properties, especially impact strength is low and wet heat resistance is poor. For this reason, when it is used for automobile parts and home appliances using general-purpose resin, there is a disadvantage that the performance of the biodegradable polyester resin is reduced before the life of the product is reached.

[0004] In order to compensate for the drawbacks of the biodegradable polyester resin represented by the polylactic acid resin, a biodegradable polyester resin and a polycarbonate resin having high heat resistance (hereinafter abbreviated as "PC resin"). May have been proposed).

[0005] For example, PA-07-109413 proposes a resin composition comprising a polylactic acid resin and an aromatic polycarbonate resin. PA-11-140292 includes a polylactic acid and a crosslinked polycarbonate. A resin composition containing the same has been proposed. In each case, the heat resistance is improved to a practical level as compared with polylactic acid alone.

[0006] Further, in order to uniformly compatibilize the polylactic acid resin with another resin, a modified olefin conjugate obtained by graft copolymerizing poly (methyl methacrylate) with a polylactic acid-based alloy resin composition is solubilized. It has been proposed for use as an agent (JP—A—2001—123055). Disclosure of the invention

Problems to be solved by the invention

According to JP-A-07-109413, it is desirable from the viewpoint of heat resistance and mechanical properties to blend an aromatic polycarbonate resin in a high proportion. Saving resources is not enough. Also, simply melting and kneading polylactic acid and polycarbonate makes it difficult to achieve uniform compatibility because the difference in melt viscosity is large.For example, the nozzle force of a kneading extruder causes the molten resin to be discharged with pulsation. However, there is a problem that stable pelletization is difficult.

[0008] JP-A-11 140292 also states that the use of cross-linked polycarbonate is desirable in terms of the effect of modifying the polylactic acid resin, and that a linear polycarbonate has a significant effect of modifying the impact resistance. Not been. In terms of moldability, polycarbonate has a higher melt viscosity than polylactic acid, so it is difficult to mold a thin material having a thickness of less than lmm. In the case of cross-linked polycarbonate, the melt viscosity is further increased, so that it is not preferable as a practical molding material.

[0009] In JP-A-2001-123055, the components that can be alloyed with polylactic acid resin are limited to aliphatic polyester resins, and therefore, there is a problem that the heat resistance is low even if the impact resistance can be improved. is there. Further, according to the present inventors, the modified olefinic conjugate used as a compatibilizer in JP-A-2001-123055 was mixed with a polylactic acid resin and a polymer alloy of PC resin or polylactic acid resin. Even when mixed with a polymer alloy of PC resin and ABS resin, the improvement in impact resistance as a compatibilizing effect was hardly obtained.

[0010] The present invention solves the above-mentioned problems, and is an alloy of polylactic acid-based biodegradable polyester resin and PC resin having excellent compatibility, and a polylactic acid-based biodegradable polymer having excellent compatibility. An alloy of a tellurium resin, a PC resin, and an ABS resin, which aims to provide a resin composition that has excellent heat resistance and impact resistance, saves oil resources, and has a low environmental impact. .

[0011] Further, it is an object of the present invention to obtain a resin composition excellent in wet heat resistance and molding processability.

Means for solving the problem

The present inventors have conducted intensive studies, and as a result, have found that a crosslinked biodegradable polyester resin and polycarbonate A resin composition comprising a resin, or a resin composition further containing an acrylonitrile Z-butadiene Z styrene copolymer resin, and a silicone compound or an ethylene Z glycidyl meta having a specific structure further added to the resin composition. The present inventors have found that the above-mentioned object is achieved by a resin composition containing a tallylate copolymer, and arrived at the present invention.

The gist of the present invention is as follows.

(1) crosslinked biodegradable polyester榭脂(A) 30- 90 wt%, polycarbonate榭脂(B) 1 0- 70 mass ^_0/0 and acrylonitrile Z butadiene-Z styrene copolymer榭脂(C) 0- 5 A resin composition comprising 0% by mass and the total of resin (A)-(C) being 100% by mass.

(2) In the resin composition of (1), the silicone resin (D) O. 05-10 parts by mass is further contained per 100 parts by mass of the total amount of the resin (Α)-(C).

(3) In the resin composition of (1) or (2), the total amount of the resin (A) — (C) is 100 parts by mass, and the modified Olefin conjugate (E) 0.1— Contains 20 parts by weight.

(4) In any one of the resin compositions (1) to (3), the mass ratio of the resins (B) and (C) is (B) / {(B) + (C)} ≥0. The relationship of 3 is satisfied.

(5) The crosslinked biodegradable polyester resin (A) is obtained by reacting the (meth) acrylate ester conjugate with 0.01 to 20 parts by mass per 100 parts by mass of the biodegradable polyester resin. The resin composition according to any one of (1) to (4)!

(6) Crosslinked biodegradable polyester resin (A) is obtained by reacting peroxide with 0.01 to 20 parts by mass per 100 parts by mass of biodegradable polyester resin from (1) The resin composition of any one of (5) to (5).

(7) Crosslinked biodegradable polyester resin The biodegradable polyester resin of (A) is mainly composed of polylactic acid or polylactic acid. Fat composition.

(8) In any one of the resin compositions of (1) to (7), the total amount of the resin (A)-(C) is 100 parts by mass, and further the carpo-imide imidized product 0.01-1-5 A resin composition containing parts by weight.

(9) The resin composition according to (8), which is a compound having an isocyanate as a terminal group in the carbodiimide bonding compound. (10) The resin composition according to any one of (1) to (9), wherein the biodegradable polyester resin of (A) is also produced from a plant-derived raw material.

(H) A molded article obtained by molding the resin composition according to any one of (1) to (10).

The invention's effect

According to the present invention, it has excellent heat resistance, impact resistance, and moist heat resistance and has a low dependence on petroleum products! A resin composition and a molded article are provided.

[0015] In particular, the combined use of PC resin and ABS resin improves the moldability (fluidity, warpage).

[0016] The resin composition of the present invention can be formed into various molded articles by injection molding or the like.

[0017] Furthermore, the resin composition of the present invention can use a natural-derived resin as a biodegradable polyester resin, so that it can contribute to the saving of depleted resources such as petroleum, and The utility value above is extremely high.

Detailed description of the invention

[0018] The resin composition of the present invention comprises a crosslinked biodegradable polyester resin (A), a polycarbonate resin (B) and, if necessary, an acrylonitrile Z butadiene Z styrene copolymer resin (C). Are mixed.

In the resin composition of the present invention, the mixing ratio of the crosslinked biodegradable polyester resin (A) as the resin component, that is, the mixing ratio, is the same as that of the resin (A)-(C) as the resin component. It is 30-90% by mass, more preferably 50-70% by mass of the total 100% by mass. When the mixing ratio of the resin (A) is less than 30% by mass, the ratio of the biodegradable raw material is reduced, and the environmental advantage is reduced. Conversely, if the amount of the resin (A) exceeds 90% by mass, physical properties such as heat resistance and impact resistance are impaired.

[0020] The crosslinked biodegradable polyester resin (A) is obtained by introducing a crosslinked structure into a biodegradable polyester resin.

[0021] Examples of the biodegradable polyester resin serving as the skeleton of the resin (A) include poly (L-lactic acid), poly (D-lactic acid), polydarcholate, polyproprolataton, polybutylene succinate, polyethylene succinate, and polybutylene. Adipate terephthalate, polybutylene succinate terephthalate and the like can be mentioned, and two or more of these may be used. Above all, heat resistance, molding In terms of properties, it is desirable to use poly (L-lactic acid), poly (D-lactic acid), or a mixture or copolymer thereof. From the viewpoint of biodegradability, it is preferable that poly (L-lactic acid) is mainly used. In addition, from the perspective of saving petroleum resources, poly (L-lactic acid), which is favored by biodegradable polyester resins produced from plant-derived raw materials, satisfies this condition.

[0022] Polylactic acid mainly composed of poly (L-lactic acid) has a different melting point depending on the ratio of the contained D-lactic acid component. In the present invention, when polylactic acid mainly composed of poly (L-lactic acid) is used, its melting point should be 160 ° C or more in consideration of the mechanical properties and heat resistance of the molded article obtained from the resin composition. Is preferred. In order to maintain a melting point of 160 ° C. or higher in poly (L-lactic acid) -based polylactic acid, it is preferable that the proportion of the D-lactic acid component is less than about 3 mol%.

[0023] There is a single biodegradable polyester resin! / ヽ means that the melt flow rate of a mixture of multiple biodegradable polyester resins at 190 ° C and a load of 21.2N is 0.1-50gZlO More preferably, it is 0.2 to 20 gZlO, more preferably 0.5 to 10 gZlO. If the melt flow rate exceeds 50 gZlO, the melt viscosity is too low, and the mechanical properties and heat resistance of the molded product may be poor. On the other hand, if the melt flow rate is less than 0.1 lgZlO, the load during molding may be too high and the operability may decrease.

[0024] The biodegradable polyester resin (A) is usually produced by a known melt polymerization method, and some of them are produced by further using a solid phase polymerization method. As a method for adjusting the melt flow rate of the biodegradable polyester resin to a predetermined range, when the melt flow rate is too large, a small amount of a chain extender, for example, diisocyanate disulfide, bisoxane A method of increasing the molecular weight of the resin using a zolini conjugate, an epoxy conjugate, an acid anhydride, or the like can be used. Conversely, if the melt flow rate is too low, a method of mixing with a biodegradable polyester resin or a low molecular weight compound having a large melt flow rate can be used.

[0025] The crosslinked structure of the crosslinked biodegradable polyester resin (A) is not particularly limited. Even if the biodegradable polyester resin molecules are directly crosslinked, they may be indirectly crosslinked via a crosslinking aid. It may be a crosslinked one or a mixture of these crosslinked structures.

[0026] As a method for introducing a crosslinked structure into the biodegradable polyester resin, an electron beam is irradiated. A known method such as a method using a polyfunctional compound such as a polyvalent isocyanate compound or the like can be applied. Above all, from the viewpoint of crosslinking efficiency, radical crosslinking by use of a peroxidic acid is preferred.

[0027] Specific examples of the peroxide include benzoyl peroxide, bis (butyl-butoxy) trimethylcyclohexane, bis (butyl-butoxy) cyclododecane, butylbis (butylperoxy) valerate, and dicumyl peroxide. Butyl peroxy benzoate, dibutyl peroxide, bis (butyl benzene) diisopropylbenzene, dimethyl di (butyl benzene) hexane, dimethyl di (butyl benzene) hexene, butyl benzocumene and the like. The amount of the peroxide is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the biodegradable polyester resin. Even if it exceeds 20 parts by mass, it can be used, but the effect is saturated and it is not economical. Since the peroxide is decomposed and consumed when mixed with the resin, even if used at the time of blending, the peroxide may not remain in the obtained resin composition.

[0028] In order to increase the cross-linking efficiency, it is preferable to use a cross-linking auxiliary agent together with the peroxide. Examples of the crosslinking assistant include dibutylbenzene, diarylbenzene, divinylnaphthalene, divinylphenol, divinylcarbazole, dibutylpyridine, and their nuclear-substituted conjugates and closely related homologues; Atharylate, butylene glycol diatalylate, triethylene glycol diatalylate, 1,6-hexanediol diatalylate, tetramethylol methane tetraatalylate, ethylene glycol dimetharate, butylene glycol dimetharate, triethylene Glycono resin methacrylate, tetraethylene glycolone dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, trimethylolpropane trimethacrylate (Meth) acrylic acid compounds such as dibutyl phthalate, tetramethylol methane tetramethacrylate, etc .; dibutyl phthalate, diaryl phthalate, diaryl maleate, bis atalilloyl xicetyl terephthalate, etc. Polybutylesters of aliphatic and aromatic polycarboxylic acids; such as polyallyl ester, polyacryloyloxyalkyl ester, polymethacryloyloxyanolequinole ester, diethylene glycol divininole ether, hydroquinone divinyl ether, and bisphenol A diaryl ether; Aliphatic and aromatic polyhydric alcohols Polybutyl ethers or polyallyl ethers; triaryl cyanurate, triallyl isocyanurate, etc., cyranuric acid or isocyanuric acid allyl ester; triallyl phosphate, trisacryloxyshethyl phosphate, N-phenylmaleimide, N, N, Polyfunctional monomers such as maleimide compounds such as m-phenylenebismaleimide; compounds having two or more triple bonds such as dipropagyl phthalate and dipropagyl maleate can be used. The amount of these crosslinking aids is not particularly limited, but is preferably 30 parts by mass or less based on 100 parts by mass of the biodegradable polyester resin from the viewpoint of effectively providing a crosslinked structure.

[0029] Among the above crosslinking assistants, (meth) acrylic acid ester conjugates are preferred from the viewpoint of crosslinking reactivity. Via this component, the biodegradable polyester resin component is crosslinked, thereby improving mechanical strength, heat resistance and dimensional stability. The (meth) acrylate ester conjugate has a high reactivity with the biodegradable resin and therefore has relatively little toxicity due to the remaining monomer, and has little coloring of the resin. Compounds having a (meth) acryl group or having at least one (meth) acryl group and at least one glycidyl group or butyl group are preferred. Specific compounds include glycidyl methacrylate, glycidyl atalylate, glycerol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triatalylate, aryloxy polyethylene glycol monoacrylate, and aryloxy polyethylene. Glycol monomethacrylate, ethylene glycol diatalate, ethylene glycol dimetharate, polyethylene glycol dimetharate, polyethylene glycol diatalylate, polypropylene glycol dimetharate, polypropylene glycol diatalylate, polytetramethylene glycol Dimetharylate, or a copolymer of an alkylene glycol in which these alkylene glycol moieties have different alkylene groups, Et al in, butanediol meth Tari rate, butanediol Atari rate or the like can be mentioned up.

When a (meth) acrylate compound is blended as a crosslinking aid, the amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the biodegradable polyester resin. 05-10 parts by weight is even more preferred 0.1-5 parts by weight is even more preferred. It can be used in excess of 20 parts by mass as long as operability is not adversely affected. [0031] As a means for mixing a crosslinking agent such as a peroxide or a crosslinking aid to the biodegradable polyester resin, a method of melt-kneading using a general extruder can be used. Wear. It is preferable to use a twin-screw extruder in order to improve the kneading state. The kneading temperature is in the range of (melting point of biodegradable polyester resin + 5 ° C)-1 (melting point of biodegradable polyester resin + 100 ° C). The kneading time is preferably 20 seconds-30 minutes. If the temperature is lower than this range or for a short time, kneading and reaction become insufficient, and if the temperature is higher or longer, decomposition or coloring of the resin may occur. When compounding, a cross-linking agent such as a peroxide or a cross-linking aid is preferably in a solid state by supplying them using a dry blend or a powder feeder. And a method of directly injecting it into the barrel of an extruder.

[0032] In a case where a crosslinking aid and a crosslinking agent such as a peroxide are used in combination, a preferred method is to dissolve or disperse the crosslinking aid and a crosslinking agent such as Z or peroxide in a medium. There is a method of injecting into a kneader. According to this, operability can be significantly improved. That is, when a biodegradable polyester resin component and a crosslinking agent such as a peroxide are melt-kneaded, a solution or dispersion of a crosslinking aid is injected, or the polyester resin component is melt-kneaded. At this time, a solution or dispersion of a crosslinking aid and a crosslinking agent such as a peroxide can be injected or melt-kneaded.

[0033] As a medium for dissolving or dispersing the crosslinking assistant and the crosslinking agent such as Z or peroxide, a general medium is used and is not particularly limited. Among them, a plasticizer excellent in compatibility with the biodegradable polyester resin according to the present invention is preferable. For example, an aliphatic polycarboxylic acid ester derivative, an aliphatic polyhydric alcohol ester derivative, an aliphatic oxyester derivative, an aliphatic polyether derivative, an aliphatic polyether polyvalent carboxylic acid ester derivative, etc. And a plasticizer. Specific compounds include glycerin diacetate monolaurate, glycerin diacetate monoforce plate, dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, acetyl methinole ricinoleate, acetinole tributynolec acid, Examples include polyethylene glycolone and dibutinole diglycol succinate. The amount of the plasticizer used as a dispersion medium is preferably 30 parts by mass or less based on 100 parts by mass of the biodegradable polyester resin. Parts by mass are more preferred. When the reactivity of the crosslinking aid or the crosslinking agent such as a peroxide is low, a plasticizer may not be used. However, when the reactivity is high, it is preferable to use 0.1 part by mass or more. Since this dispersion medium may volatilize when mixed with the resin, it may not remain in the obtained resin composition even when used in the production.

[0034] The component of the polycarbonate resin (B) in the present invention is a repeating unit composed of a bisphenol group residue and a carbonate residue.

Examples of the starting bisphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibutene 4-hydroxyphenyl) propane, and 2,2-bis (3,5-Dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane Xan, 1,1-bis (4-hydroxyphenyl) decane, 1,4-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4'- Dihydroxydiphenyl ether, 4,4 'dithiodiphenol, 4,4' dihydroxy-3,3'-dichlorodiphenyl ether, 4,4 'dihydroxy-2,5-dihydroxydiphenyl ether and the like. . In addition, diphenols described in U.S. Pat. Nos. 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used. These may be used alone, or some may be used in combination of two or more.

[0036] Examples of the precursor for introducing the carbonate residue unit include phosgene and diphenyl carbonate.

[0037] The intrinsic viscosity of the polycarbonate resin (B) is preferably in the range of 0.40 to 0.64. If it exceeds 0.64, the melt viscosity of the resin composition may be so high that kneading extrusion or injection molding may be difficult. On the other hand, if it is less than 0.40, the impact strength of the obtained molded product may be insufficient.

[0038] The mixing ratio of the polycarbonate resin (B) is 10 to 70% by mass in the total amount of the resins (A) and (C) of 100% by mass. When the content of the resin (B) is less than 10% by mass, the heat resistance and impact resistance of the obtained resin composition are insufficient, and when it exceeds 70% by mass, the dependence of the raw material on petroleum resources is high. As a result, the degree of environmental contribution is low.

[0039] In the resin composition of the present invention, the above-mentioned crosslinked biodegradable polyester resin (A) and In addition to polycarbonate resin (B) and acrylonitrile Z butadiene Z styrene copolymer resin (C) may be used. By adding the resin (C), the fluidity of the obtained resin composition at the time of molding is increased, and the residual strain inside the molded article is reduced, so that the warpage of the molded article can be reduced. Further, the appearance of the molded article can be made excellent.

[0040] The mixing ratio of the resin (C) is in the range of 0 to 50% by mass relative to the total amount of the resin (A)-(C) of 100% by mass. Further, the relationship between the mixing ratios of the resins (B) and (C) preferably satisfies (B) / {(B) + (C)} ≥0.3 by mass ratio. When the ratio of the polycarbonate resin (B) to the total amount of the resin (B) and the resin (C) satisfying this formula is 0.3 or more, the heat resistance of the obtained resin composition is improved. Impact resistance is further improved.

[0041] Acrylonitrile Z butadiene Z styrene copolymer resin (C) is a resin generally referred to as "ABS resin" as described above, and contains an aliphatic conjugated diene monomer as an essential component. In the presence of 5 to 70% by mass of a rubbery polymer obtained by polymerizing monomers, a monomer containing a cyanide vinyl monomer and an aromatic vinyl monomer as essential components 30 to 95 It is a graft copolymer obtained by polymerizing mass%.

[0042] Examples of the aliphatic conjugated gen used herein include 1,3-butadiene, isoprene, and chloroprene. In particular, 1,3-butadiene can be preferably used from the viewpoint of impact resistance. The ratio of the aliphatic conjugated diene monomer is preferably 30 to 100 parts by mass based on 100 parts by mass of the total of the monomers used for producing the rubbery polymer. By setting the ratio to 30 parts by mass or more, a graft copolymer having good impact resistance can be obtained.

[0043] When an aliphatic conjugated diene monomer and another monomer are used in combination as the monomer used for producing the rubbery polymer, the other monomer is a diene monomer. Various monomers copolymerizable with the polymer can be used. Specific examples thereof include a cyanide-based monomer such as acrylonitrile and metal-tol-tolyl; an aromatic-based monomer such as styrene, _α -methylstyrene, ρ-chlorostyrene, and ρ-methylstyrene; acrylic acid Examples include unsaturated carboxylic esters such as methyl, ethyl acrylate, η-butyl acrylate, 2-ethylhexyl acrylate, η-xysyl acrylate, methyl methacrylate, and ethyl methacrylate. As described above, the monomer to be graft-polymerized to the rubber-like polymer contains vinyl cyanide-based monomer and aromatic vinyl-based monomer as essential components. Specific examples of the vinyl cyanide-based monomer include acrylonitrile, metharyl-tolyl, cyanidani biylidene, and the like. Among them, acrylonitrile is particularly preferred. Specific examples of the aromatic vinyl monomer include butyltoluenes such as styrene, α-methylstyrene and ρ-methylstyrene, halogenated styrenes such as ρ-chlorostyrene, ρ-t-butylstyrene, dimethylstyrene, and styrene. -Lunaphthalenes and the like. Of these, styrene and α-methylstyrene are particularly preferred.

[0045] As monomers for graft polymerization, in addition to vinyl cyanide-based monomers and aromatic vinyl-based monomers, other monomers can be used in combination, if desired. Specific examples thereof include unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate, η-butyl acrylate, 2-ethylhexyl acrylate, η-xyl acrylate, methyl methacrylate, and ethyl methacrylate. Unsaturated monomers such as maleic anhydride, itaconic anhydride and citraconic anhydride; maleimide, Ν-methylmaleimide, Ν-butylmaleimide, Ν-phenylmaleimide, Ν-cyclohexylmaleimide, etc. And an imide compound of an unsaturated dicarboxylic acid. These may be used alone or in combination of two or more.

[0046] These monomers are usually used in a ratio of 100% of the total mass to 100% of the total amount of cyanide vinyl monomer / aromatic vinyl monomer / other monomer (mass ratio) = 10— 50 / 50-90Ζ0-40, preferably 15 45Ζ55 85Ζ020.

[0047] Further, the monomers for graft polymerization include, as necessary, glycidyl methacrylate, methacrylic acid, acrylic acid, methacrylamide, 2-hydroxyethyl methacrylate, and polyethylene glycol monomethacrylate. It is also possible to use 20% by mass or less, preferably 15% by mass or less based on the total of 100% by mass of the monomers for graft polymerization.

[0048] In the production of the graft copolymer, the ratio of the rubbery polymer and the monomer mixture for graft polymerization was, as described above, the ratio of the rubbery polymer to the monomer mixture (mass ratio) = 5-70. / 30-95, preferably 1065-3590. When the amount of the rubber-like polymer is less than 5% by mass, the proportion of the rubber-like polymer in the resin is inevitably reduced, and the impact resistance is reduced. Meanwhile, 70 If the mass is more than ⁰ / o, the graft ratio to the rubber-like polymer becomes low, and the dispersion of the rubber-like polymer in the resin becomes insufficient, so that impact resistance cannot be exhibited.

When a metal catalyst is used during the polymerization of acrylonitrile Z butadiene Z styrene copolymer resin, it is preferable to remove the metal catalyst after the polymerization. This is because the metal catalyst promotes the hydrolysis of the biodegradable polyester resin, and may lower the wet heat resistance.

[0050] In the resin composition of the present invention, the resin (A)-(C) as each component may be mixed at a predetermined ratio in the final resin composition. ,. The mixing order and mixing method are not particularly limited. For example, the resin raw materials of the components (A), (B) and (C) may be melt-mixed simultaneously, or two of them may be mixed first, and then the other may be mixed. It is good. While mixing, the polycarbonate resin (B) and the acrylonitrile Z-butadiene Z-styrene copolymer resin (C) may be mixed in advance prior to blending the crosslinked biodegradable polyester resin (A). preferable. By doing so, the fluidity of the final resin composition during molding can be further improved, and the appearance of the molded article can be improved. As the mixture of the polycarbonate resin (B) and the acrylonitrile Z-butadiene Z-styrene copolymer resin (C), commercially available ones can also be used.

[0051] The resin composition of the present invention can further improve the impact resistance performance by blending the silicone conjugate (D). The silicone conjugate is a polymer having a siloxane bond unit (formula 1). R SiO (formula 2) as a basic unit is a linear polymer.

2

Even if a unit has a branched structure by introducing RSiO (Formula 3) or SiO (Formula 4) units

1.5.2.0

Good.

01 in

C

Place) 0053

£ 0052

(ε) — ο— ί s—〇一

[ε ^] [οο] l.9T00 / S00Zdf / X3d 179SS.0 / S00Z OAV [0055] [Formula 4]

—〇一 S i —〇一 (4)

However, if the number of branches is too large, it becomes difficult for the silicone compound to be uniformly dispersed in the biodegradable polyester resin and the polycarbonate resin, so that an excessively branched structure is not preferred. The type of the organic group R bonded to the silicon other than the main chain is not particularly limited, and any known organic group can be used. For example, generally, a methyl group, a phenyl group, and hydrogen are mentioned. In addition, a modified silicone compound modified with an organic functional group such as an epoxy group, an amino group, an alcohol group, or a carboxyl group, or an alkyl group, a polyether, or a higher fatty acid ester can also be used. Further, two or more of these may be used in combination. However, when bleed-out of the silicone compound becomes a problem in the molded product or when heat resistance is required, the point of compatibility with the methylphenylsilicone conjugate material is also desirable.

The terminal group of the polymer is not particularly limited, and those having a methyl group, a phenyl group, and other functional groups can be used. [0058] The trade names of these silicone conjugates are exemplified. Examples of dimethyl silicone include the TSF451 series from GE Toshiba Silicone, KF96, KF96L, KF96H, KF69, KF92, KF961, KF961, KF965, and KF968 from Shin-Etsu Silicone. And so on. Examples of methylphenol silicone include GE Toshiba Silicone's TSF431, TSF433, TSF434, TSF437, TSF4300, and Shin-Etsu Silicone's KF50, KF54, and KF56. No. Examples of methyl hydrogen silicone include "TSF484" from GE Toshiba Silicone and "KF99" from Shin-Etsu Silicone. Epoxy-modified silicone oils include "TSF4730" from GE Toshiba Silicones, "KF100T", "KF101", "KF102" and "KF103" from Shin-Etsu Silicones. Amino-modified silicones include GE Toshiba Silicone's TSF4700, TSF4701, TSF4702, TSF47 03, TSF4704, TSF4705, TSF4706, TSF4707, TSF4708, and TSF4708. TSF4709 "and Shin-Etsu Silicone's" KF857 "," KF858 "," KF859 "," KF861 "," KF864 ", and" KF880 ". An example of alcohol-modified silicone is Shin-Etsu Silicone's “KF851”. Examples of carboxyl-modified silicone include GE Toshiba Silicone's "TSF4770" and Shin-Etsu Silicone's "X-22-3710" and "-22-370 ^". Examples of the alkyl-modified silicone oil include “TS F4421” and “XF42-A3161” manufactured by GE Toshiba Silicone.

[0059] When the silicone conjugate is blended, the amount is 0.05-10 parts by mass per 100 parts by mass of the total amount of the resins (A)-(C). If the amount is less than 0.05 part by mass, the effect of improving the impact resistance is poor. If the amount exceeds 10 parts by mass, bleed-out tends to occur, and the heat resistance tends to decrease.

[0060] In the resin composition, by using the modified Olefin conjugate (E) as a compatibilizer, the compatibility can be enhanced and the impact resistance can be further improved. The modified resin conjugate in the present invention is obtained by graft copolymerization of poly (meth) acrylate, poly (meth) acrylate, glycidyl methacrylate copolymer, polystyrene, acrylonitrile z styrene copolymer and the like. Add the olefin compound. Examples of the olefin conjugate include polyethylene, ethylene Z glycidyl methacrylate copolymer, ethylene Z ethyl acrylate copolymer, ethylene Z butyl acetate copolymer, and ethylene ethyl acrylate. Water maleic acid copolymer and the like can be mentioned. In particular, ethylene Z glycidyl methacrylate copolymer obtained by graft copolymerization of poly (methyl methacrylate) and poly (methyl methacrylate) Z-glycidyl methacrylate copolymer is excellent in impact resistance. Specific examples of the trade names of the ethylene Z glycidyl methacrylate copolymer obtained by graft copolymerization of poly (methyl methacrylate) include “MODIPA A4200”, “AT13100”, and “AT13130” manufactured by NOF Corporation. A specific trade name of an ethylene Z glycidyl methacrylate copolymer obtained by graft copolymerization of a poly (methyl methacrylate) Z glycidyl methacrylate copolymer is, for example, "AT13110" of Nihon Yushi Co., Ltd.

[0061] The compounding amount of the modified olefin conjugate (E) is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the resins (A) to (C). If the amount is less than 0.1 part by mass, the effect of compatibilization is hardly exhibited. If the amount exceeds 20 parts by mass, the heat resistance may be reduced.

[0062] A carbodiimide compound can be blended with the resin composition. The moist heat resistance of the resin composition is improved by including the carpoimide compound, and a crosslinked structure is introduced between the crosslinked biodegradable polyester resin (A) and the polycarbonate resin (B). The compatibility becomes better, and the mechanical properties of the resin composition also improve. Examples of the carbodiimide compound include 4,4'-dicyclohexylmethanecarbodiimide, tetramethylxylylenecarbodiimide, N, N-dimethylphenylcarbodiimide, and N, N'-di-2,6-diisopropylphenylcarbodiimide. It is not particularly limited as long as it is a carbodiimide compound having one or more carbodiimide groups in a force molecule.

[0063] As the carbodiimide compound, a compound in which the terminal isocyanate group is sealed with a monoisocyanate or the like may be used, but the moist heat resistance and mechanical properties (particularly, impact resistance) of the resin composition are improved. From this viewpoint, it is preferable to use a carbodiimide compound having an isocyanate group left. The isocyanate group has higher reactivity than the carbodiimide group, and a higher effect is obtained.

[0064] The carbodiimide compound can be produced by a conventionally known method, and can be produced by a carbodiimide reaction accompanied by a decarbonation reaction using a diisocyanate compound as a raw material. At this time, if the terminal blocking treatment is not performed, a carbodiimide conjugate having an isocyanate group at the terminal is obtained. [0065] The amount of the carbodiimide compound is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 13 parts by mass, per 100 parts by mass of the total amount of the resins (A) and (C). If the amount is less than 0.01 parts by mass, the effect of improving the wet heat resistance and the mechanical properties is not obtained, while if it exceeds 5 parts by mass, the heat resistance may be reduced.

[0066] In producing the resin composition, the method of mixing the raw materials is not particularly limited, as long as each component is uniformly dispersed in the resin composition. For example, cross-linked biodegradable polyester resin (A), polycarbonate resin (B), acrylonitrile Z butadiene Z styrene copolymer resin (C), silicone resin conjugate (D), modified olefin resin Compound (E) and the like are uniformly blended using a tumbler or Henschel mixer, and then melt-kneaded to pelletize.

For more uniform dispersion, pellets in which two or more types of raw materials are melt-kneaded may be used. For example, a composition obtained by melt-kneading or copolymerizing a polycarbonate resin (B) and a silicone conjugate (D), or a composition obtained by mixing a polycarbonate resin (B) with acrylo-tolyl Z butadiene Z styrene Use a composition obtained by melt-kneading the system copolymer resin (C).

[0068] In the case of using a carbodiimide compound, it is preferable to melt and knead other resin raw materials, and to melt and knead the mixture at a stage where the compatibility has progressed to some extent. When melt kneading is performed at the same time, the compatibilization between other raw material components, especially when an ethylene Z glycidyl methacrylate copolymer grafted with poly (meth) acrylate is used, the compatibilization reaction due to this component occurs. May be inhibited. As an example of the mixing operation, the raw materials other than the carpoimide conjugate are once melt-kneaded with an extruder, and then the carpo-imide conjugate is added and then melt-kneaded again, or extruded by a side feeder or the like. For example, a method of adding a carbodiimide compound in the middle of the machine.

[0069] An organic or inorganic filler may be added to the resin composition for the purpose of improving mechanical strength and heat resistance. The compounding amount is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin composition.

[0070] Examples of the inorganic filler include glass fibers, metal fibers, carbon fibers, metal whiskers, ceramic whiskers, fibrous reinforcing materials such as potassium titanate, talc, calcium carbonate, and charcoal. Zinc oxide, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite, Hydrate Talcite, boron nitride, graphite. Examples of the organic filler include naturally occurring polymers such as starch, fine cellulose particles, wood flour, okara, fir husk, bran and kenaf, and modified products thereof.

[0071] Above all, glass fibers, which are preferred by fibrous reinforcing materials, are most preferable because they can improve heat resistance and impact resistance. The glass fiber is preferably subjected to a surface treatment in order to enhance the adhesion to the resin component. As a method of adding the fibrous reinforcing material, the hopper force may be added to the extruder at the same time as the other raw materials, or the intermediate force of the kneading machine may be added using a side feeder. In addition, a master resin filled with a fibrous reinforcing material at a high concentration is prepared, and the master resin can be diluted with a base resin at the time of molding to be used so as to have a desired concentration.

[0072] The resin composition has a pigment, a heat stabilizer, an anti-oxidation agent, a weathering agent, a light-proofing agent, a flame retardant, a plasticizer, a lubricant, a mold release agent, as long as its properties are not significantly impaired. An antistatic agent, a crystal nucleus material and the like can be added. Examples of the heat stabilizer and the anti-oxidizing agent include hindered phenols, phosphorus-containing compounds, hindered amines, zeo compounds, copper compounds, alkali metal halides, and vitamin E. As the flame retardant, a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant can be used. However, in consideration of the environment, it is preferable to use a non-halogen flame retardant. Examples of non-halogen flame retardants include phosphorus flame retardants, hydrated metal compounds (aluminum hydroxide, magnesium hydroxide), N-containing compounds (melamine-based, guadin-based), and inorganic compounds. (Borate, Mo compound). Examples of the inorganic crystal nucleus material include talc and phosphorus, and examples of the organic crystal nucleus material include a sorbitol compound, benzoic acid and a metal salt of the compound, a phosphate metal salt, and a rosin compound. The method of mixing these with the resin composition is not particularly limited.

[0073] The resin composition of the present invention may be formed into various molded articles by a molding method such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, air pressure molding, and vacuum pressure molding after sheet processing. Can be. In particular, the injection molding method is generally preferred In addition to the injection molding method, molding methods such as gas injection molding and injection press molding can be adopted. Injection molding conditions suitable for the resin composition of the present invention vary depending on the resin composition ratio, but it is appropriate that the cylinder temperature is in the range of 180 to 260 ° C, more preferably 190 to 250 ° C. is there . The mold temperature should be 140 ° C or less. If the cylinder temperature is too low, the operability becomes unstable, such as short-circuiting of the molded product, or it tends to overload.On the other hand, if the cylinder temperature is too high, the resin composition will decompose, In some cases, problems such as a decrease in the strength of the obtained molded body and coloring of the molded body may occur.

The heat resistance of the molded article made of the resin composition of the present invention can be enhanced by promoting crystallization by controlling the conditions during injection molding and performing heat treatment after molding. As a method for this, for example, there is a method of promoting crystallization by cooling in a mold during injection molding. In this case, it is preferable to cool the mold for a predetermined time while keeping the mold temperature at the crystallization temperature of the resin composition ± 20 ° C. In consideration of the releasability of the mold force, the mold temperature may be further lowered to the glass transition temperature of the resin composition or lower, and then the mold may be opened to remove the molded product. As a method of accelerating crystallization after molding, it is preferable to heat-treat the obtained molded article again at a crystallization temperature of ± 20 ° C. If there are multiple crystallization temperatures, the same treatment is performed at each temperature. If there are multiple glass transition temperatures, there is no problem in molding! / ヽ Select the glass transition temperature. .

[0075] Specific examples of the molded body include resin parts for electric shading products such as a personal computer housing, a printer housing, and a projector lamp housing, and automotive resins such as bumpers, inner panels, and door trims. Parts and the like. Further, it may be a film, a sheet, a hollow molded article, or the like.

Example

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following embodiments.

1.Evaluation items

(1) Melt flow rate (MFR):

According to JIS K7210 (test condition 4), the measurement was performed at 190 ° C and a load of 21.2N.

(2) Intrinsic viscosity (IV): The measurement was carried out at a temperature of 20 ° C. using a phenol Zl, 1,2,2-tetrachloroethane mixed solvent (mass ratio 6Z4).

(3) Heat distortion temperature (DTUL):

Measured at a load of 0.45 MPa according to ASTM standard D-648. Test specimens were prepared as follows. In other words, using an injection molding machine (TOSHIBA MACHINE IS-80G), the resin is melted at a cylinder temperature of 210-240 ° C, and the injection pressure is 100MPa, the injection time is 15 seconds and the mold is 70 ° C. Fill and cool for 30 seconds.

However, the polylactic acid resin was cooled for 20 seconds at a cylinder temperature of 190 ° C., an injection pressure of 100 MPa, an injection time of 10 seconds, and a mold temperature of 30 ° C.

[0078] Regarding the crosslinked polylactic acid resin or the crosslinked polylactic acid Z polybutylene succinate resin, the cylinder temperature was 190 ° C, the injection pressure was 100MPa, the injection time was 15 seconds, the mold temperature was 100 ° C, and the cooling was performed for 60 seconds. .

(4) Impact strength (IZOD impact strength):

According to ASTM standard D-256, the measurement was performed using a test piece with a notch (V-shaped notch). The test piece was obtained by the same molding method as in (3).

(5) Flexural modulus:

According to ASTM standard D-790, it was measured with a load applied at a deformation speed of ImmZ. Test pieces were obtained by the same molding method as in (3).

(6) Bending strength:

(7) Moisture and heat resistance:

The bending strength test piece obtained in (6) was treated for 800 hours in an environment of a temperature of 60 ° C and a humidity of 95% RH, and then the bending strength was measured. .

(8) Liquidity:

Using a bar-shaped mold with a thickness of lmm, molding is carried out using an injection molding machine (Toshiba Machine Co., IS-80G) at a cylinder temperature of 220 ° C, a mold temperature of 70 ° C, and an injection pressure of lOOMPa. Flow The moving length (mm) was measured. The molding conditions of polylactic acid, crosslinked polylactic acid or crosslinked polylactic acid Z-polybutylene succinate resin were in accordance with (3). The larger the flow length, the better the fluidity.

(9) Warpage:

A molding test of a square plate was performed (a square is a film gate, and a mold having a thickness of 60. Omm x 60.0 mm x a thickness of lmm was used). The molding temperature was set at 220 ° C and the mold temperature was set at 70 ° C. The molding conditions for polylactic acid, crosslinked polylactic acid, or crosslinked polylactic acid Z polybutylene succinate resin conformed to (3). Injection speed · Injection pressure was set so that the molding shrinkage was 0.2%. The obtained flat molded product was placed on a horizontal table with the convex side facing up, and the height was measured. The amount of warpage was evaluated as (warpage height) Z (length of flat plate diagonal) X 100 (%). If this value is 0.5% or less, it can be determined that there is no practical problem with the molded product.

( ₁₀ ) Compound operability:

The state at the time of compounding was observed and evaluated as follows.

〇: Nozzle force of extruder The molten resin is discharged without pulsation, and the step of continuously pelletizing with a pelletizer that does not break the strand can be performed without any problem.

Δ: Nozzle force of extruder Molten resin is discharged with pulsation, and strands are easily cut. The process up to pellet cutting may be interrupted.

(11) Molded product appearance:

The appearance of the molded product was observed and classified as follows.

〇: The unevenness is almost inconspicuous.

Δ: unevenness is conspicuous

X: The unevenness is very conspicuous.

2. Raw materials

(1) Polylactic acid resin:

Cargill Dow's Nature Works 6201DK; MFR = IOgZlO content, melting point 168 ° C (hereinafter abbreviated as “PLA”).

(2) Cross-linked polylactic acid resin:

It was prepared as follows. [0083] Using a twin-screw extruder (TEM-37BS, manufactured by Toshiba Machine Co., Ltd.), the top feeder force was also supplied with PLA, and melt kneading and extrusion were performed at a processing temperature of 190 ° C. At that time, 1.0 part by mass of polyethylene glycol dimethalate (manufactured by NOF Corporation) as a crosslinking aid (hereinafter abbreviated as “PEGDM”) and tert-butyl peroxide (NOF Corporation) as a crosslinking agent A solution in which 1.0 mass part was dissolved in 2.5 parts by mass of a glycerin diacetomonola force plate as a plasticizer was injected from the middle of the kneader using a pump. The discharged resin was cut into pellets to obtain a crosslinked biodegradable polyester resin (hereinafter, abbreviated as “crosslinked PLA”). The MFR of the obtained crosslinked PLA was 1.2 gZlO.

(3) Cross-linked polylactic acid Z polybutylene succinate resin:

It was prepared as follows.

[0084] Using a twin-screw extruder (TEM-37BS, manufactured by Toshiba Machine Co., Ltd.), PLA and polybutylene succinyl resin (GS-Pla AZ-71T, manufactured by Mitsubishi Iridaku Co., Ltd.) were combined (PLA). Chips mixed at a mass ratio of / (polybutylene succinate resin) = 90ZlO were also supplied with the top feeder force, and were melt-kneaded and extruded at a heating temperature of 190 ° C. At that time, 0 parts by mass of PEGD Ml. As a cross-linking aid and 1.0 parts by mass of di-t-butyl peroxide (manufactured by NOF Corporation) as a cross-linking agent were combined with glycerin diacetomonola resin as a plasticizer. The solution dissolved in 2.5 parts by mass of the plate was injected using a pump from the middle of the kneader. The discharged resin was cut into pellets to obtain a cross-linked polylactic acid Z-polybutylene succinate resin (hereinafter, abbreviated as “cross-linked PLAZPBSJ”. The MFR of the obtained cross-linked PLAZPBS was 1. The content was 5 gZlO.

(4) PC resin:

200-13 manufactured by Sumitomo Dow (IV = 0.49).

(5) mixture of PC榭脂ZABS榭脂(PC榭脂ratio of about 40 weight ^_0/0):

Sumitomo Dow IM-6100 (hereinafter abbreviated as "PCZABS").

(6) Ethylene glycidyl methacrylate copolymer obtained by graft copolymerization of poly (methyl methacrylate):

MODIPER A4200 manufactured by NOF Corporation (hereinafter abbreviated as “EGMA-gf-PMMA”).

(7) Silicone compound: • GE Toshiba Silicone Methyl Feel Silicone Oil TSF-433

• Shin-Etsu Silicone Co., Ltd.

• GE Toshiba Silicone Amino-modified silicone oil TSF4707

• Epoxy-modified silicone oil TSF4730 manufactured by GE Toshiba Silicone

• GE Toshiba Silicone's hydroxy-terminated methylphenol silicone YF3804

(8) Carposimidii conjugate:

• Nisshinbo LA-1; isocyanate group content 13%

• Nisshinbo HMV—8CA; isocyanate-based encapsulated product

Example 11

Each raw material was supplied to a twin-screw extruder (TEM-37BS, manufactured by Toshiba Machine Co., Ltd.) at the ratios shown in Tables 1, 3, and 4, where it was melt-kneaded at a processing temperature of 220 ° C to 240 ° C and extruded. The resin was cut into pellets to obtain a resin composition A-HH. All the raw materials were supplied at the same time from the top feed port, except that the raw material was supplied by side feed when the carbodiimide compound was added.

Comparative Example 11

Each raw material is supplied to a twin-screw extruder (TEM-37BS, manufactured by Toshiba Machine Co., Ltd.) at the ratios shown in Table 2-4, melt-kneaded at a processing temperature of 210 ° C-230 ° C, and extruded. Was cut into pellets to obtain a resin composition II-1UU. In this case, in Comparative Examples 1, 2, 4, 8, 12, and 13, the nozzle resin was also discharged while the molten resin was pulsating, and it was difficult to perform pellet siding. In Comparative Examples 6 and 7, the resin raw material was directly used for injection molding for preparing various test pieces.

[0085] Tables 14 to 14 summarize the results of the evaluation of various physical properties.

[0086] In Examples 1 to 34, a resin composition having excellent DTUL and IZOD impact strength was obtained. In addition, the following is clear.

[0087] PLA has almost no improvement in IZOD impact strength when crosslinked by itself (Comparative Examples 6 and 7). Melt kneading of uncrosslinked PLA and PC results in poor operability. On the other hand, when the PLA is cross-linked and further melt-kneaded with PC, the operability is improved, and at the same time, the IZOD impact strength is significantly improved (comparison between Example 1 and Comparative Example 1). [0088] By blending the ABS component, the fluidity is improved, the amount of warpage is reduced, and the appearance is improved. The DTUL and IZOD impact strengths are also better than the PLA alone component (Examples 3-7, 10, 11).

[0089] By blending the silicone ridge, the IZOD impact strength is improved (Examples 13 to 24). In addition, the effect of improving the impact strength is observed in various silicone conjugates (Examples 13 to 17). Such an effect is small in Comparative Example 8 in which the PLA is not crosslinked and Comparative Example ₉ in which the amount of the crosslinked PLA is out of the range of the present invention.

[0090] The addition of EGMA-gf-PMMA improved the IZOD impact strength! / Puru (Example 2)

5—34). These effects are small in Comparative Examples 12 and 13 in which the PLA is not crosslinked and Comparative Examples 10 and 11 in which the amount of the crosslinked PLA is out of the range of the present invention.

[0091] When the silicone compound is used in combination with EGMA-gf-PMMA, the IZOD impact strength is further improved (Examples 28, 29 and 31).

[0092] The moist heat resistance is improved by the addition of a carpoimide compound (Examples 8-12, 20, 29)

, 33). Carposimidized conjugates having an isocyanate group are useful for improving heat and moisture resistance.

It has the effect of also improving the OD impact strength (comparing Examples 8 and 12).

[0093] Comparative Examples 2 and 4 are obtained by adding a carbodiimide conjugate to the composition of Comparative Example 1, and the operability of melt kneading is improved as compared with Comparative Example 1, but PLA is crosslinked. ,,, For

The IZOD impact strength is low and impractical.

[0094] In Comparative Examples 3 and 5, the proportion of PC was too small, so that the DTUL and IZOD impact strength were hardly improved.

[0095] [Table 1]

Table 1 Example Example Example Example Example Example Example Example Example Example Example Example Example

1 2 3 4 5 6 7 8 9 10 1 1 12 Shear yarn Fiber A B C D E F G H 1 J κ Shi Makoto Resin component PLA

(Frame iSPLA 50 70 50 70 50 70 50 70 50 70 50 frame ^ S LVPBS 50

PC 50 30 30 18 50 30 50

ABS 20 12

PC / ABS (40/60) 50 30 50 50 30 Silicone TSF433

Compound KF54

TSF4707

TSF4730

YF3804

EGMA-gf ^ PMMA

Polymer

Karposi LA- 1 1.5 1.5 1.5 1.5 Mid compound H V-8CA 1.5 Compound operability 〇〇 O 〇〇 O 〇 0 〇〇〇〇 Physical properties DTUL (.C) 126 114 95 83 99 88 94 123 111 95 85 122 Bending ¾ ) S (MPa) 113 1 16 92 100 93 102 84 1 16 120 96 108 1 15 Flexural modulus (GPa) 3.2 3.7 2.9 3.3 2.9 3.3 2.4 3.3 3.7 3.0 3.5 3.3

EOD Return bow jeal (J / m) 98 65 65 54 62 50 75 125 72 71 52 105 Moisture and heat resistance (%) 57 38 39 35 43 33 45 100 100 100 100 90 Warpage (%) 0.10 0.08 0.06 0.06 0.07 0.06 0.06 0.11 0.08 0.08 0.06 0.11 Flowability (mm) 87 1 10 120 136 115 134 125 81 101 108 127 79 Appearance of molded product

Table 2 Honorable Thighs Fine J; 瞧麵 Rows 麵 Rows 1 2 3 4 5 6 7 Resin Seiko U JJ KK LL MM NN 00 Makoto Resin Component PLA 50 50 50 100

(Mass part) Frame ίΐΡ 95 95 100 Frame ilPLA / PBS

PC 50 50 5 5

ABS

PC / ABS (40/60) 50

Silicone TSF433

Compound

[S KF54

¾0097 TSF4707

TSF4730

YF3804

GERMAFT-EGMA-gf-PMMA

Polymer

Carbodi-1 1.5 1.5 1.5 Mid compound HMV-8GA

Compound's operability 〇 O 〇〇--Physical properties DTUL (° C) 123 121 61 92 63 57 74 Flexural strength (MPa) 105 1 13 125 91 121 121 129 Flexural modulus (GPa) 2.9 3.0 4.4 2.7 4.3 3.8 4.7

IZOD impact jewel (J / m) 31 35 28 31 29 26 24 Moisture / heat resistance (./.) 52 85 37 76 29 0 0 Warpage (%) 0.09 0.10 0.05 0.07 0.05 0.05 0.05 Property (mm) 110 106 127 135 138 209 142 Molded product appearance X X X X X

Table 3

(U dimension 8600

Table 4

Claims

The scope of the claims

[1] cross biodegradable polyester榭脂(A) 30- 90 wt ^_0/0, polycarbonate榭脂(B) 10 one 70 mass ^_0/0 and acrylonitrile Z butadiene-Z styrene copolymer榭脂(C) 0- A resin composition containing 50% by mass, wherein the total of resin (A)-(C) is 100% by mass.

[2] The method according to claim 1, wherein the silicone resin conjugate (D) further contains 0.05-10 parts by mass per 100 parts by mass of the total amount of the resin (A)-(C). Fat composition.

[3] The composition according to claim 1, further comprising 0.1 to 20 parts by mass of the modified Olefin conjugate (E) per 100 parts by mass of the total amount of the resins (A) to (C). The resin composition according to 1 or 2

[4] The mass ratio between the resin (B) and the resin (C) satisfies the relationship of (B) Z {(B) + (C)} ≥0.3. The resin composition according to item 1, wherein

[5] Cross-linked biodegradable polyester resin (A) strength obtained by reacting (meth) acrylic acid ester conjugate with 0.01 to 20 parts by mass per 100 parts by mass of biodegradable polyester resin The resin composition according to any one of claims 1 to 4, characterized in that:

[6] Crosslinked biodegradable polyester resin (A) converts peroxide to biodegradable polyester resin 1

6. The resin composition according to claim 1, wherein the resin composition is obtained by reacting 0.01 to 20 parts by mass per 100 parts by mass.

[7] The biodegradable polyester resin of the crosslinked biodegradable polyester resin (A) is polylactic acid! / ヽ is mainly composed of polylactic acid. either

Item 4. The resin composition according to Item 1.

[8] The method according to any one of claims 1 to 7, further comprising 0.01 to 5 parts by mass of the carbodiimidized conjugate with respect to 100 parts by mass of the total amount of the resins (A) to (C). The resin composition according to item 1.

[9] The resin composition according to [8], wherein the carbodiimide compound is a compound having an isocyanate as a terminal group.

[10] The method according to any one of claims 1 to 9, wherein the biodegradable polyester resin of the crosslinked biodegradable polyester resin (A) is produced from a plant-derived material. Record The resin composition described above.

A molded article obtained by molding the resin composition according to any one of claims 1 to 10.