JP5233063B2 - Resin composition and molded article comprising the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a resin composition having an excellent impact strength and a white appearance without pearl luster, a resin composition exhibiting high flame retardancy, and a molded article comprising the same.

  Polylactic acid resin is expected as a practically excellent biodegradable polymer because it has a high melting point and can be melt-molded. In addition, in the future, it is expected to be used as a general-purpose polymer made from bio raw materials, and various molded products are formed by injection molding, extrusion molding, and the like.

  On the other hand, cellulose derivatives such as cellulose and cellulose esters and cellulose ethers are expected to be the most biodegradable polymers produced from bio raw materials on the earth, and in the same way as polylactic acid resins, there are various types of cellulose derivatives such as injection molding and extrusion molding. It is a molded product.

  However, polylactic acid resins and cellulose esters have the disadvantage that they are inferior in impact resistance and are brittle, and that they are slightly inferior in whiteness.

  In addition, aromatic polycarbonate resins are excellent in transparency, impact resistance and mechanical properties, and are used for many purposes as transparent products and industrial products. ing.

  Patent Document 1 proposes blending polylactic acid as a method of modifying the fluidity of the aromatic polycarbonate resin. However, since the obtained material has a pearly luster, its application is limited, and there is a problem that the ballast effect is easily caused during melt-kneading and the productivity is poor.

  Patent Document 2 proposes blending an aromatic polycarbonate resin in order to improve the by-cut softening point of polylactic acid resin.

  Patent Document 3 proposes blending polycarbonate to improve the impact resistance of polylactic acid resin.

  Patent Document 4 proposes a composition having excellent foamability in which a polyisocyanate compound is blended with a polylactic acid resin, polycarbonate, polystyrene, or the like.

  Patent Document 5 proposes a medical material in which a polyfunctional triazine compound is blended with a polymer such as polylactic acid resin, cellulose, and polycarbonate.

  Patent Document 6 proposes a fiber material in which a polylactic acid resin and a polymer compound, and a cellulose ester and a polymer compound are blended.

  Patent Document 7 proposes a composition excellent in optical characteristics in which cellulose ester and polycarbonate are blended.

  Patent Document 8 proposes that a cellulose ester or a polycarbonate resin is blended with a polylactic acid resin and a polyacetal resin as other thermoplastic resins.

  However, the compositions of Patent Documents 2 to 8 have a problem that they are difficult to be made into any one of impact strength, pearly luster, and whiteness performance or flame retardancy.

  Here, melt mixing two or more kinds of polymers is widely known as a polymer blend or a polymer alloy, and is widely used as a method for modifying the defects of individual polymers. However, in many cases where two or more kinds of polymers are melt-mixed, the strands are separated into individual phases due to differences in viscosity, molecular weight, molecular structure, etc., and have a coarse dispersion structure. In many cases, it is difficult to pelletize, and mixing unevenness due to phase separation is observed on the surface of the obtained injection-molded product, which may cause pearl luster, surface peeling and generation of flow marks on the appearance of the molded product.

  The polylactic acid resin and polycarbonate of the present invention, cellulose ester and polycarbonate, and the polymer blend of polylactic acid resin, cellulose ester, and polycarbonate also have a phase separation structure that separates into individual phases. Mixing unevenness due to phase separation is observed on the surface of the obtained injection-molded product, which is presumed to cause the above-mentioned pearly luster, surface peeling and flow mark.

  As a method for improving such phase separation, blending the following compatibilizing agent has been proposed.

  Patent Document 9 proposes melting and mixing a radical reaction initiator in a polylactic acid resin and polycarbonate under a nitrogen atmosphere.

  In Patent Document 10, a polymer compound containing an organometallic compound and / or a methacrylic resin unit by grafting or copolymerization is added as a compatibilizing agent to improve the compatibility between a polylactic acid resin having a weight average molecular weight of 50,000 or more and a cellulose ester. It is effective that a resin composition having excellent transparency, mechanical properties, and heat resistance can be obtained. Further, Patent Document 10 further includes other thermoplastic resins as long as the object of the invention is not impaired. However, no mention is made of polycarbonate, and a transparent material is obtained as the reason. It is assumed that it is difficult.

  Moreover, since polylactic acid resin and cellulose ester are easily flammable by themselves, they cannot be used for members that require flame retardancy. On the other hand, the aromatic polycarbonate resin is known as a material that is harder to burn than polylactic acid resin and cellulose ester. However, a polymer blend composition of a polylactic acid resin and one or a mixture of cellulose esters is easily combusted and therefore cannot be used for a member that needs to be flame retardant.

Patent Document 1, Patent Document 7, Patent Document 8 and Patent Document 10 disclose that a flame retardant can be blended with a polylactic acid resin or the like. Specific means for obtaining high flame retardancy There was no disclosure.
Japanese Patent No. 3279768 (page 1-2), (paragraph number [0008]) US Pat. No. 5,300,576 (EXAMPLE1) JP-A-11-140292 (page 1-2) JP 2000-17038 A (page 1-2) JP 2003-695 A (page 1-2) Japanese translation of PCT publication No. 2003-532804 (page 1-2) JP2003-306577A (page 1-2), (paragraph number [0052]) JP 2003-342460 A (page 1-2), (paragraph number [0053]) JP 2002-371172 A (page 1-2) JP 2004-204217 A (paragraph numbers [0020] to [0027], [0044], [0043])

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Therefore, an object of the present invention is to provide an appearance excellent in impact strength and excellent in whiteness without pearly luster, comprising a polylactic acid resin and one or a mixture of cellulose esters, an aromatic polycarbonate resin and a compatibilizing agent. Another object of the present invention is to provide a resin composition having a high degree of flame retardancy, and a molded product comprising the resin composition having a flame retardant.

  The inventors of the present invention provide a resin composition comprising one or more resins selected from polylactic acid resins and cellulose esters, an aromatic polycarbonate resin and a compatibilizing agent, and a resin composition containing a flame retardant, as described above. It has been found that it has excellent characteristics that meet the objectives of the present invention, and has reached the present invention.

That is, the present invention
(1) One or more resins selected from (A) polylactic acid resin and (B) cellulose ester, 75 to 10% by weight; (C) aromatic polycarbonate resin from 25 to 90% by weight; and (b) and (b) below Resin composition comprising 1 to 50 parts by weight of at least one (D) compatibilizer selected from (A) and (B) and 100 parts by weight of the total amount of component (C). Product (however, (C) composition ratio (B parts by weight) of polylactic acid resin per 100 parts by weight of aromatic polycarbonate resin and (b) composition ratio (C parts by weight) of talc with an average particle size of 5 μm or less And excluding an aromatic polycarbonate resin composition in a range satisfying the following formula (I)
0.3 × B ≦ C (I)),
(B) an average particle size of 5μm or less of talc (b) anhydride grafted or copolymerized ethylene copolymer (2) wherein is (B) a cellulose ester, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate Pro The resin composition according to (1) , which is at least one cellulose ester selected from the group consisting of pionate, cellulose acetate butyrate, and cellulose acetate phthalate.
(3) It further comprises (E) one or more flame retardants selected from brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants ( 1) to the resin composition according to any one of (2) ,
(4) The resin composition according to (3) , wherein the phosphorus flame retardant of the flame retardant (E) is a phosphate ester,
(5) The resin composition according to any one of (1) to (4) , further comprising (F) a fluororesin.
(6) The resin composition according to any one of (1) to (5) , further comprising (G) an epoxy compound.
(7) Further, (H) (A) polylactic acid resin, (B) cellulose ester, (C) polycarbonate resin and (F) polyester resin which is a thermoplastic resin other than fluororesin , polyamide resin, styrene resin, and The resin composition according to any one of (1) to (6) , comprising one or more thermoplastic resins selected from silicone compound-containing core-shell rubbers ,
(8) The resin composition according to any one of (1) to (7) , further comprising (I) a fiber reinforcement.
(9) The resin composition according to any one of (1) to (8) , further comprising (J) a layered silicate.
(10) The resin composition according to any one of (1) to (9) , further comprising (K) a plasticizer.
(11) A molded article comprising the resin composition according to any one of (1) to (10) .

  The resin composition of the present invention has an external appearance excellent in impact strength and excellent in whiteness without pearly luster, and further has high flame retardancy by blending a flame retardant. The molded article of the present invention comprising this resin composition can be effectively used for various applications such as mechanical mechanism parts, electrical / electronic parts, building members, automobile parts, and daily necessities, making use of the above-mentioned properties.

  Hereinafter, the present invention will be described in detail.

  The (A) polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such other copolymerization component is preferably 0 to 30 mol%, and preferably 0 to 10 mol%, based on all monomer components.

  In the present invention, it is preferable to use a polylactic acid resin (A) in which the optical purity of the lactic acid component is high from the viewpoint of compatibility. That is, (A) Of the total lactic acid components of the polylactic acid resin, it is preferable that the L-form is contained in 80% or more, or the D-form is contained in 80% or more, and the L-form is contained in 90% or more or It is particularly preferably 90% or more, more preferably 95% or more of L isomer or 95% or more of D isomer, 98% or more of L isomer, or 98% or more of D isomer. More preferably.

  It is also preferable to use a polylactic acid containing 80% or more of L-form and a polylactic acid containing 80% or more of D-form. It contains 90% or more of polylactic acid containing 90% or more of L-form and D-form. It is more preferable to use polylactic acid in combination.

  (A) The polylactic acid resin may be modified, for example, by using maleic anhydride-modified polylactic acid resin, epoxy-modified polylactic acid resin, amine-modified polylactic acid resin, etc., not only heat resistance, The mechanical properties tend to be improved, which is preferable.

  (A) As a manufacturing method of a polylactic acid resin, a well-known polymerization method can be used, and the direct polymerization method from lactic acid, the ring-opening polymerization method via a lactide, etc. can be mentioned.

  (A) The molecular weight and molecular weight distribution of the polylactic acid resin is not particularly limited as long as it can be practically processed, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more. Furthermore, it is desirable that it is 80,000 or more. The upper limit is preferably 350,000 or less from the viewpoint of fluidity during molding. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  (A) Although it does not restrict | limit especially about melting | fusing point of a polylactic acid resin, It is preferable that it is 120 degreeC or more, and also it is preferable that it is 150 degreeC or more. (A) Since the melting point of the polylactic acid resin tends to increase as the optical purity increases, the polylactic acid resin having a high melting point may be a polylactic acid resin having a high optical purity.

  The (B) cellulose ester in the present invention refers to a cellulose hydroxyl group blocked by an esterifying agent. Specific esterifying agents include acid bases such as acetyl chloride and propionyl chloride, acid anhydrides such as acetic anhydride, pyropionic acid and butyric anhydride, carboxylic acid compound derivatives such as amide compounds and ester compounds, and ε- And cyclic esters such as caprolactone.

  Specific cellulose ester types include cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate. (A) Compatibility or miscibility with polylactic acid resin From the viewpoint of properties, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate are preferable, and cellulose triacetate and cellulose acetate propionate are more preferable. Moreover, it is preferable that the substitution degree of the hydroxyl group in cellulose (average number of hydroxyl groups substituted by cellulose ester) is 0.5 to 2.9 per glucose unit. In addition, from the viewpoint of better compatibility or miscibility with (A) polylactic acid resin, the degree of substitution is preferably 1.5 to 2.9, and more preferably 2.0 to 2.8. More preferred. Moreover, said substitution degree can be calculated | required by using and esterifying the esterifying agent produced | generated by alkaline hydrolysis to a high performance liquid chromatography.

  The aromatic polycarbonate resin (C) in the present invention includes aromatic polycarbonate such as aromatic homo or copolycarbonate obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester.

  Examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.

  The blending amount of the components (A) to (C) is one or more resins 75 to 10 selected from (A) polylactic acid resin and (B) cellulose ester with respect to 100% by weight of the total of components (A) to (C). (C) aromatic polycarbonate resin 25 to 90% by weight, (A) one or more resins selected from polylactic acid resin and (B) cellulose ester 70 to 15% by weight, (C) aromatic polycarbonate resin It is preferably 30 to 85% by weight, 65% to 20% by weight of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester, and (C) 35 to 80% by weight of aromatic polycarbonate resin. It is particularly preferred.

  In the present invention, by blending (C) an aromatic polycarbonate resin, the whiteness, impact strength and heat resistance of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester are modified. (C) If the blending amount of the aromatic polycarbonate resin is less than 25% by weight, the above-mentioned modification effect is insufficient, and if the blending amount of the (C) aromatic polycarbonate resin exceeds 90% by weight, a transparency is obtained. Since it becomes too strong, it is not preferable. In the present invention, when the component (A) and the component (B) are used in combination, the blending ratio is arbitrary, but the ratio of (A) to (B) is 1/9 to 9/1 from the viewpoint of moldability. It is preferable that the ratio is 2/8 to 8/2.

  The (D) compatibilizing agent in the present invention is one for compatibilizing one or more resins selected from (A) polylactic acid resin and (B) cellulose ester with (C) aromatic polycarbonate resin. Here, when the component (C) is melt-kneaded with one or more resins selected from the components (A) and (B) without blending the compatibilizer of the component (D), the ballast effect is greatly melted. There is a problem that the strand cannot be drawn and it becomes difficult to form a pellet, or there is a problem that the appearance of the surface of the molded product is greatly impaired due to pearl luster, surface peeling, and flow mark, and this is because (A) component and / or (B) component (C ) The components are presumed to be produced because they are not compatible but are coarsely dispersed. The (D) compatibilizing agent in the present invention has a function of modifying the compatibility of the components (A) and / or (B) and the component (C) to finely disperse them.

Such (D) a compatibilizer, an average particle diameter of 5μm or less of talc, acid anhydride grafted or copolymerized ethylene copolymer is cited, may be used in one kind or two or more.

  Moreover, the compounding amount of the compatibilizer is 50 parts by weight to 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. 1 part by weight is preferable, more preferably 40 parts by weight to 3 parts by weight, and particularly preferably 30 parts by weight to 4 parts by weight. If the amount is less than 1 part by weight, the effect as a compatibilizer is small. This is not preferable because the mechanical properties are deteriorated.

The lower limit of the average particle size of the talc having an average particle size of 5 μm or less is preferably an average particle size of 0.5 μm or more from the viewpoint of handleability during production, and is preferably an average particle size of 1 μm or more. More preferred.

The talc is preferably used because the obtained molded product has high whiteness. The average particle diameter is measured by a 50% cumulative distribution average particle diameter measured by a laser diffraction scattering method.

The blending amount of talc having an average particle size of 5 μm or less is based on 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. 50 parts by weight to 1 part by weight is preferable, more preferably 40 parts by weight to 3 parts by weight, and particularly preferably 30 parts by weight to 4 parts by weight. When the amount is less than 1 part by weight, the effect as a compatibilizer is small, and 50 parts by weight. Exceeding the portion is not preferable because the mechanical properties deteriorate.

Preferred examples of the acid anhydride in the ethylene copolymer obtained by grafting or copolymerizing the above acid anhydride include maleic anhydride.

Further , the amount used when grafting or copolymerizing the acid anhydride to the polymer compound is not particularly limited, but it is 0.05% by weight or more and 20% by weight or less with respect to the ethylene copolymer. Is preferable, and 0.1 to 5% by weight is more preferable.

An acid anhydride as a grafted or copolymerized ethylene copolymer is not limited, used in one or more selected from among it. Further, examples of d styrene copolymer, ethylene and a monomer, as the copolymerizable monomer propylene, butene-1, vinyl acetate, isoprene, butadiene or acrylic acid, monocarboxylic acids, or of these, such as methacrylic acid ester acids, maleic acid, copolymers prepared from dicarboxylic acids such as fumaric acid or itaconic acid. also used preferably further polymeric compound grafted with methyl methacrylate, et styrene / propylene -g- maleic anhydride Acid, ethylene / glycidyl methacrylate, ethylene ethyl acrylate-g-maleic anhydride, ethylene / butene 1-g-maleic anhydride, ethylene / ethyl acrylate / maleic anhydride-g-polymethyl methacrylate, ethylene / glycidyl methacrylate- g Such as methyl methacrylate and the like as part of the specific examples ( "- / -" represents copolymerized, "- g-" represents the graft following the same..).

The blending amount of the ethylene copolymer containing an acid anhydride by grafting or copolymerization is the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester (C) aromatic polycarbonate resin. 50 parts by weight to 1 part by weight is preferable with respect to 100 parts by weight, more preferably 40 parts by weight to 3 parts by weight, particularly preferably 30 parts by weight to 4 parts by weight, and less than 1 part by weight as a compatibilizer. The effect is small, and if it exceeds 50 parts by weight, the heat resistance and mechanical properties are greatly deteriorated.

  The (E) flame retardant used in the present invention is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin. Specifically, brominated flame retardants and phosphorus-based flame retardants are used. Examples include flame retardants, nitrogen compound flame retardants, silicone flame retardants, and other inorganic flame retardants, and at least one of these can be selected and used.

  Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, Tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and a generally used phosphorus-based flame retardant can be used. Typically, an organic phosphorus compound such as a phosphate ester or a polyphosphate, , Red phosphorus.

  Specific examples of the phosphoric acid ester in the above organic phosphorus compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl. Phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl Phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acetate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include condensed phosphate esters such as diethyl, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. be able to. Examples of commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR747 manufactured by Daihachi Chemical Co., Ltd. In particular, a condensed phosphate represented by the following formula (1) can be preferably used from the viewpoint of hydrolyzability.

（上式において、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４は、同一または相異なる、ハロゲンを含有しない芳香族基を表す。また、Ｘは下記の（２）〜（４）式から選択される構造を示し、下記（２）〜（４）式中、Ｒ^１〜Ｒ^８は同一または相異なる水素原子または炭素数１〜５のアルキル基を表し、Ｙは直接結合、Ｏ、Ｓ、ＳＯ_２、Ｃ（ＣＨ_３）_２、ＣＨ_２、ＣＨＰｈを表し、Ｐｈはフェニル基を表す。また、（１）式のｎは０以上の整数である。また、（１）式のｋ、ｍはそれぞれ０以上２以下の整数であり、かつ（ｋ＋ｍ）は０以上２以下の整数である。）なお、かかる芳香族縮合リン酸エステルは、異なるｎや、異なる構造を有する芳香族縮合リン酸エステルの混合物であってもよい。

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is selected from the following formulas (2) to (4): In the following formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, n in the formula (1) is an integer of 0 or more, and k and m in the formula (1) are Each of them is an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.) In addition, such aromatic condensed phosphates are different n or aromatic condensed phosphates having different structures. It may be a mixture of

  In the formula of the formula (1), n is an integer of 0 or more, and the upper limit is preferably 40 or less from the viewpoint of flame retardancy. Preferably it is 0-10, Most preferably, it is 0-5.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a neopentyl group. However, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

  Of these, the following compounds (5) and (6) are preferable, and the compound (5) is particularly preferable.

  Moreover, the phosphate and polyphosphate which consist of a salt with phosphoric acid, polyphosphoric acid, a metal of group IA-IVB of the periodic table, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts, triazine salts, melamine salts, and ammonium salts.

  In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond. Examples thereof include phosphazene compounds and phosphoric ester amides.

  Further, as red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. It can be preferably used. The thermosetting resin of the thermosetting resin film is not particularly limited as long as it is a resin capable of coating red phosphorus. For example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin Etc. The metal hydroxide coating is not particularly limited as long as it can coat red phosphorus, and examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. . The metal of the metal plating film is not particularly limited as long as it can coat red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.

  Examples of the nitrogen compound-based flame retardant used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like. . In addition, nitrogen-containing phosphorus flame retardants such as ammonium polyphosphate as exemplified in the above phosphorus flame retardant are not included in the nitrogen compound flame retardant referred to herein. Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. Examples of the aromatic amine include aniline and phenylenediamine. Examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide include N, N-dimethylacetamide. Examples of aromatic amides include N, N-diphenylacetamide.

  The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. And thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.

  As melamine cyanurate or melamine isocyanurate, an addition product of cyanuric acid or isocyanuric acid and a triazine compound is preferable, usually an addition having a composition of 1 to 1 (molar ratio) and optionally 1 to 2 (molar ratio). You can list things. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Moreover, the average particle diameter before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 1 μm from the viewpoint of flame retardancy, mechanical strength, and surface property of the molded product.

  Of the nitrogen compound-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, among which triazine compounds are preferable, and melamine cyanurate is more preferable.

  When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as polyvinyl alcohol or metal oxide may be used in combination. Good.

Examples of the silicone flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

  Other inorganic flame retardants used in the present invention include magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, oxidation Metal of tin salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, tungstic acid Examples thereof include salts, complex oxide acids of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, graphite, and swellable graphite. Of these, aluminum hydroxide, zinc borate, and swellable graphite are preferable.

  The above (E) flame retardant may be used alone or in combination of two or more. When aluminum hydroxide is used, one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin are previously kneaded and melt mixed at a kneading temperature of 210 ° C. or less. And preferably used.

  (E) The amount of the flame retardant is 100 to 0.00 with respect to 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. 5 parts by weight, more preferably 80 to 1 part by weight.

  Among the above (E) flame retardants, a combination of at least one or two or more selected from phosphorus-based flame retardants containing no halogen, nitrogen compound-based flame retardants, silicone-based flame retardants and other inorganic flame retardants Are preferably used. In the above, when two or more flame retardants are used in combination, it is preferable to use a phosphorus-based flame retardant together with another flame retardant. The nitrogen compound-based flame retardant used in combination with the phosphorus-based flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and further preferably melamine cyanurate. Moreover, as a silicone type flame retardant used together with a phosphorus type flame retardant, a silicone resin is preferable. Moreover, as other inorganic flame retardants used in combination with phosphorus flame retardants, aluminum hydroxide, zinc borate and swellable graphite are preferable. Further, the blending ratio with the phosphorus-based flame retardant can be combined with any amount, and the amount of the phosphorus-based flame retardant in 100% by weight of the flame retardant is particularly preferably 5% by weight or more, and 5 to 95% by weight. It is more preferable that

  The (F) fluorine-based resin in the present invention is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, etc. Polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene Fluoride is preferred, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are particularly preferred, polytetrafluoroethylene is more preferred, and polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer The body is also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer, and the like. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is from 0.1% by weight to 90%. It is preferable that it is weight%.

  The blending amount of the (F) fluorine-based resin is based on 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. It is 3-0.01 weight part, Preferably 2-0.02 weight part is preferable, More preferably, 1-0.03 weight part is preferable. When the blending amount of the fluororesin exceeds 3 parts by weight, the extrusion moldability and flame retardancy of the present invention are adversely decreased. When the blending amount is less than 0.01, no effect is found in improving the flame retardancy.

  In the present invention, (G) an epoxy compound can be further blended.

  The epoxy compound (G) used in the present invention may be a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound, but is preferably an epoxy compound having a glycidyl group, such as a glycidyl ester compound. , Glycidyl ether compounds, and glycidyl ester ether compounds. One or more of these epoxy compounds can be used.

  Further, the glycidyl ester compound is not limited, but as specific examples, glycidyl benzoate, glycidyl tBu-benzoate, glycidyl P-toluate, glycidyl cyclohexanecarboxylate, glycidyl pelargonate Ester, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl bersate, glycidyl oleate, glycidyl linoleate, glycidyl linoleate, glycidyl behenol, stearolic acid Glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester , Naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester , Succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, and the like. Two or more kinds can be used.

  The glycidyl ether compound is not limited, but specific examples include phenyl glycidyl ether, P-phenylphenyl glycidyl ether, 1,4-bis (β, γ-epoxypropoxy). ) Butane, 1,6-bis (β, γ-epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1 Others such as-(β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and bis- (4-hydroxyphenyl) methane Examples include diglycidyl ether obtained by the reaction of bisphenol and epichlorohydrin. These may be used alone or in combination. Can.

  The (G) epoxy compound preferably used is an epoxy compound in which a monofunctional glycidyl ester compound and a glycidyl ether compound are used in combination, or a monofunctional glycidyl ester compound, more preferably a composition capable of obtaining a monofunctional glycidyl ester compound. Excellent balance between viscosity stability and hydrolysis resistance.

  Moreover, the epoxy equivalent of (G) epoxy compound is preferably an epoxy compound of less than 500, more preferably an epoxy compound of less than 400 epoxy equivalent. Here, the epoxy equivalent is an epoxy compound in which the number of grams of an epoxy compound containing 1 gram equivalent of an epoxy group is less than 500, and the epoxy equivalent is obtained by dissolving the epoxy compound in pyridine, adding 0.05N hydrochloric acid and adding 45N After heating, a mixture of thymol blue and cresol red is used as an indicator and back titration with 0.05N caustic soda can be used.

  In addition, (G) the epoxy compound has a great effect on improving the hydrolyzability without inhibiting the viscosity stability and mechanical properties, and the compounding amount of the epoxy compound is from the viewpoint of the viscosity stability and hydrolyzability, ( 10 to 0.01 parts by weight, preferably 9 to 0.1 parts by weight per 100 parts by weight of the total amount of one or more resins selected from A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. 05 parts by weight, more preferably 8 to 0.1 parts by weight. The epoxy compound does not include a polymer compound obtained by grafting or copolymerizing a glycidyl compound.

  In the present invention, an alkaline earth metal compound can be further blended.

  Preferred alkaline earth metal compounds in the present invention include alkaline earth metal compounds such as magnesium compounds, calcium compounds, and barium compounds. Examples of the alkaline earth metal compounds include hydroxides, oxides, carbonates, sulfates, acetates, acetates, lactates, oleic acid, palmitic acid, stearic acid, and montanic acid of alkaline earth metals. And organic acid salts. Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate. , Barium sulfate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and magnesium, calcium and barium salts of organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid Is mentioned. Among these, hydroxides and carbonates of alkaline earth metals are preferably used. In particular, magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. Such alkaline earth metals can be used alone or in combination of two or more. In addition, calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. are known depending on the production method. Included in the invention. These alkaline earth metal compounds may be treated with one or more surface treatment agents such as silane coupling agents, organic substances and inorganic substances, and the shape may be powder, plate or fiber. From the viewpoint of dispersibility, it is preferable to use it in a powder form having an average particle size of 10 μm or less. Further, if the particle size is fine, the effect of improving hydrolyzability is large and preferable.

In addition, as an effect of blending an alkaline earth metal compound, a flame retardant, particularly a phosphorus flame retardant, is easily hydrolyzed, which adversely affects the hydrolyzability of the polylactic acid resin. By adding a metal compound in combination, the hydrolyzability is further improved by neutralizing the phosphoric acid generated from the hydrolyzed phosphorus-based flame retardant with an alkaline earth metal compound. Presumed. In addition, when an alkali metal compound is used instead of the alkaline earth metal compound, the alkali metal compound is not preferred because it often has alkalinity and usually promotes hydrolysis of the polylactic acid resin. The alkaline earth metal compound used in the present invention is preferably insoluble in water in a neutral state and exhibits a neutralizing action by dissolving in an acidic environment when the phosphate ester is decomposed and the system becomes acidic. Used. The solubility in the neutral state is described in, for example, the Handbook of Chemistry, published by Maruzen Co., Ltd. (Showa 41), and the solubility in water is preferably 1 g / 100 g or less, more preferably 10 ⁻¹ g / 100 g water or less. Incidentally, the solubility of calcium carbonate most preferably used in water is 5.2 × 10 ⁻³ g / 100 g water.

  Moreover, the compounding quantity of an alkaline-earth metal compound is 1 type or more resin chosen from (A) polylactic acid resin and (B) cellulose ester, and (C) aromatic polycarbonate resin from the surface of a mechanical characteristic and hydrolyzability. It is 10-0.01 weight part with respect to 100 weight part of total amounts, Preferably it is 9-0.05 weight part, More preferably, it is 8-0.1 weight part.

In the present invention, (H) (A) a polylactic acid resin, (B) a cellulose ester , ( C) a polycarbonate resin, and (F) a thermoplastic resin other than a fluororesin can be blended. Specific examples of the resin include a polyester resin, a polyamide resin, a styrene resin, and a silicone compound-containing core-shell rubber .

  Moreover, said (H) thermoplastic resin may be used by 1 type, or may be used in combination of 2 or more types.

  The blending amount of the (H) thermoplastic resin is 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) polycarbonate resin. It is 200-0.5 weight part, Furthermore, it is preferable that it is 150-1 weight part.

  The polyester resin preferably used in the above (H) thermoplastic resin is (i) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, (b) hydroxycarboxylic acid or its ester-forming property. It is a polymer or copolymer obtained by polycondensation of one or more selected from derivatives, (c) lactones, and is a thermoplastic polyester resin other than polylactic acid resin.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acid units such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like And La ester forming derivatives.

  Examples of the hydroxycarboxylic acid include glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and ester formation thereof. Sex derivatives and the like. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Specific examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene terephthalate, polypropylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), bisphenol A (Terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polypropylene (terephthalate / naphthalate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate) Phthalate), poly (cyclohexanedimethylene / ethylene) terephthalate , Aromatic polyesters such as poly (cyclohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, and polybutylene (terephthalate / succinate) ), Polypropylene (terephthalate / succinate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polyethylene ( Terephthalate / sulfoisophthalate / succinate), polypropylene ( Phthalate / sulfoisophthalate / succinate), polybutylene (terephthalate / sebate), polypropylene (terephthalate / sebate), polyethylene (terephthalate / sebate), polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polyethylene terephthalate / polyethylene glycol, poly Butylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene) Oxide) glycol , Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polypropylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polybutylene (terephthalate / isophthalate) / Poly (propylene oxide / ethylene oxide) glycol, Polypropylene (terephthalate / isophthalate)・ Poly (propylene oxide / ethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polybutylene terephthalate, poly-ε-caprolactone, etc. Polymer, polyethylene oxalate, polypropylene oxalate, poly Tylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polybutylene adipate, polypropylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polypropylene (succinate / adipate), polyethylene ( Succinate / adipate), polyhydroxyalkanoates such as polyhydroxybutyric acid and copolymers of β-hydroxybutyric acid and β-hydroxyvaleric acid, aliphatic polyesters such as polycaprolactone, polyglycolic acid, fats such as polybutylene succinate carbonate Group polyester carbonate, p-oxybenzoic acid / polyethylene terephthalate, p-oxybenzoic acid / 6-o Shi-2 liquid crystalline polyesters such as copolyesters, such as naphthoic acid ( "/" indicates copolymerization. same as below. ).

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components is preferable. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polypropylene naphthalate, polybutylene naphthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene (terephthalate / isophthalate), polybutylene terephthalate・ Polyethylene glycol, polypropylene terephthalate ・ Polyethylene glycol, polyethylene terephthalate ・ polyethylene glycol Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, Polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polypropylene (terephthalate / succinate) , Polyethylene (terephthalate / succinate It can be mentioned preferably. Ratio of aromatic dicarboxylic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of the above aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components Is more preferably 30 mol% or more, and particularly preferably 40 mol% or more.

  Among these, a polymer obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, or butanediol or an ester-forming derivative thereof as a main component is more preferable. Specifically, polypropylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate・ Poly (tetramethylene oxide) glycol, polypropylene terephthalate ・ Poly (teto Methylene oxide) glycol, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate) / Isophthalate) poly (tetramethylene oxide) glycol, polyethylene (terephthalate / succinate), polyethylene (terephthalate / adipate), polypropylene (terephthalate / succinate), polypropylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polybutylene ( Terephthalate / adipate) That. The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 30 mol% or more. More preferably, it is particularly preferably 40 mol% or more.

  Preferred examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / succinate), polyester elastomer, polypropylene terephthalate. , Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene succinate, and particularly preferred examples include polybutylene terephthalate, polypropylene terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene ( Terephthalate / succinate), polybutylene sac At least one selected from the acid can be used, and may be used alone or in combination of two or more. By blending a polyester resin, flame retardancy, moldability, heat resistance A resin composition and a molded product with improved properties and mechanical properties can be obtained.

  The polyamide resin used in the present invention is a thermoplastic polymer having an amide bond starting from amino acid, lactam or diamine and dicarboxylic acid.

  Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. Examples of lactam include ε-caprolactam and ω-laurolactam.

  Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3, 8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Piperazine, Ami Such as ethyl piperazine, and the like.

  Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

  Preferred polyamides used in the present invention include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon). 6/10), polyhexamethylene dodecamide (nylon 6/12), polyundecane adipamide (nylon 11/6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexa Methylene terephthalamide, polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl) -4-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T (H )) And copolymers thereof with these polyalkylene glycols, mixed polyamides, polyamide elastomers, and the like. Among these, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 11/6 and copolymer polyamides such as copolymerization of these with polyethylene glycol, mixed polyamide, Polyamide elastomer is preferable, nylon 6, nylon 11, nylon 12, nylon 6 / polyethylene glycol, and polyamide elastomer are more preferable, and nylon 6 and nylon 6 / polyethylene glycol are particularly preferable.

  Further, from the problem of thermal stability of (A) polylactic acid resin, (B) cellulose ester and (C) polycarbonate resin, the melting point of the polyamide resin used is preferably 90 ° C. or higher and 240 ° C. or lower, and 100 ° C. or higher. More preferably, it is 230 degrees C or less.

  Said polyamide resin may be used independently and may be used in mixture of 2 or more types.

  In the present invention, a resin composition and a molded product in which the moldability, mechanical characteristics, and heat resistance of the resin composition of the present invention are modified can be obtained by blending the polyamide resin.

  The styrenic resin in the present invention is a (co) polymer containing styrene, and is an aromatic vinyl compound such as α-methylstyrene, vinyltoluene, and divinylbenzene, a vinyl cyanide compound such as acrylonitrile, methyl methacrylate, methacrylic acid. (Meth) acrylic acid alkyl esters such as ethyl acetate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide , Maleimide monomers such as N-cyclohexylmaleimide, diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, vinyl alkyl ethers, ethylene, diene rubbers (eg polybutadiene (Polyisoprene, polychloroprene) and the like may be further copolymerized, and specific examples of (co) polymers containing styrene include, but are not limited to, polystyrene resins, impact polystyrene resins ( High impact polystyrene resin), acrylonitrile / styrene copolymer (hereinafter abbreviated as AS resin), ABS resin, acrylate / styrene / acrylonitrile copolymer (AAS resin), acrylonitrile / ethylene / styrene (AES resin), styrene / butadiene copolymer Polymer (SB resin), styrene / butadiene / styrene copolymer (SBS resin), styrene / ethylene / butylene / styrene copolymer (SEBS resin), styrene / isoprene / styrene copolymer (SIS resin), etc. In particular, AS resin is preferably used. The

  The amount of styrene and acrylonitrile as main components in the preferably used AS resin is preferably at least 70% by weight or more, and the copolymerization ratio of styrene and acrylonitrile is 10% or more and less than 50% by weight. The amount of acrylonitrile is preferable, and the amount of acrylonitrile of 20% by weight or more and less than 40% by weight is more preferable. When the acrylonitrile content is in an appropriate range, particularly when a phosphorus-based flame retardant is used, a resin composition excellent in bleeding resistance and a molded product can be obtained.

  Preferable examples of the silicone compound-containing core-shell rubber include silicone / acrylic composite core-shell rubber.

  In the present invention, (I) a fibrous reinforcing material can be further blended to improve heat resistance, particularly heat distortion temperature.

  As the (I) fibrous reinforcing material used in the present invention, those usually used for reinforcing thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, sepiolite, asbestos, slag fiber, zonolite, elestite, plaster Fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber and other inorganic fibrous reinforcements, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie Organic fibrous reinforcements such as cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper waste, waste paper and wool Among these (I) fiber reinforcements, inorganic fibrous reinforcement Material is preferred, especially glass Wei and aluminum borate whisker are preferred. The use of organic fibrous reinforcing materials is also preferable, and natural fibers and regenerated fibers are more preferable from the viewpoint of taking advantage of the biodegradability of polylactic acid resin and cellulose ester, and kenaf is particularly preferable. Further, the aspect ratio (average fiber length / average fiber diameter) of the fibrous reinforcing material used for blending is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

  The (I) fibrous reinforcing material may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, such as aminosilane or epoxysilane. It may be treated with a coupling agent or the like.

  Moreover, the compounding quantity of (I) fibrous reinforcement is 100 weight part of the total amount of 1 or more types of resin chosen from (A) polylactic acid resin and (B) cellulose ester, and (C) aromatic polycarbonate resin. 200 to 0.1 parts by weight, preferably 100 to 0.5 parts by weight.

  In the present invention, (J) layered silicate can be further blended, and formability can be improved. Further, (J) the layered silicate is more preferably blended with a layered silicate in which exchangeable cations existing between the layers are exchanged with organic onium ions. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is the exchange of the exchangeable cation of the layered silicate having the exchangeable cation between the layers with the organic onium ion. Inclusion compound.

  A layered silicate having an exchangeable cation between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 angstroms are laminated. Has a cation. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

  (J) Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. Swellable mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., which may be natural or synthesized. . Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. The ammonium ion may be any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium, and examples of the primary ammonium ion include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, and benzyl ammonium. Examples of secondary ammonium ions include methyldodecylammonium and methyloctadecylammonium. Examples of tertiary ammonium ions include dimethyldodecylammonium and dimethyloctadecylammonium. Examples of quaternary ammonium ions include benzyltrimethylammonium, benzyltriethylammonium, Benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyl Benzyltrialkylammonium ions such as utadecylammonium and benzalkonium, alkyltrimethylammonium ions such as trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium, dimethyldialkyl such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium Examples thereof include ammonium ions, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, and benzethonium ions having two benzene rings. In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group. Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more.

  Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  (J) Layered silicate in which exchangeable cations existing between layers used in the present invention are exchanged with organic onium ions reacts layered silicates having exchangeable cations between layers and organic onium ions by a known method. Can be manufactured. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or melted ammonium salt may be used.

  In the present invention, the amount of the organic onium ions relative to the (J) layered silicate is such that the dispersibility of the (J) layered silicate, the thermal stability during melting, the gas during molding, and the suppression of odor generation J) The cation exchange capacity of the layered silicate is usually in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents.

  In addition to the above organic onium salts, these (J) layered silicates are preferably pre-treated with a coupling agent having a reactive functional group to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the blending amount of (J) layered silicate is based on 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) polycarbonate resin. 40-0.1 weight part is preferable, 30-0.5 weight part is further more preferable, and 10-1 weight part is especially preferable.

  In the present invention, (K) a plasticizer can be further blended.

  As the (K) plasticizer used in the present invention, known ones generally used as polymer plasticizers can be used without any particular limitation. For example, polyester plasticizers, glycerin plasticizers, polyvalent carboxylate esters Examples thereof include a plasticizer, a polyalkylene glycol plasticizer, and an epoxy plasticizer.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Trimellitic acid esters such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and sebacic acid esters such as di-2-ethylhexyl sebacate and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, polyacrylic acid esters, and paraffins. The (K) plasticizer used in the present invention is preferably at least one selected from polyester-based plasticizers and polyalkylene glycol-based plasticizers, among those exemplified above, and may be used in combination of two or more. Good.

  The blending amount of (K) plasticizer is 30 with respect to 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. The range is preferably -0.01 parts by weight, more preferably 20-0.1 parts by weight, and particularly preferably 10-0.5 parts by weight.

  In the present invention, it is preferable to add (K) a plasticizer because moldability and heat resistance are improved without impairing flame retardancy.

  In the present invention, a crystal nucleating agent can be further blended. Examples of the crystal nucleating agent include known inorganic nucleating agents such as nitrides, organic nucleating agents such as organic carboxylic acid metal salts, sorbitols, and ( A) A polymer nucleating agent having a melting point higher than that of the polylactic acid resin may be mentioned.

  The compounding amount of the crystal nucleating agent is 30 to 0 with respect to 100 parts by weight of the total amount of one or more resins selected from (A) polylactic acid resin and (B) cellulose ester and (C) aromatic polycarbonate resin. 0.01 parts by weight is preferred, 10 to 0.05 parts by weight is more preferred, and 5 to 0.1 parts by weight is particularly preferred.

  In the present invention, it is preferable to add a crystal nucleating agent because moldability and heat resistance are improved.

  In the present invention, (K) the plasticizer and the crystal nucleating agent may be used alone, but it is preferable to use both in combination in terms of moldability.

  In the present invention, the resin is adjusted to various colors by adding one or more kinds of pigments and dyes of carbon black, titanium oxide, petal, ultramarine blue, calcined yellow, and various colors, and weather resistance (light) The blending amount of the pigment and the dye may be one or more resins selected from (A) a polylactic acid resin and (B) a cellulose ester, and (C) an aromatic polycarbonate resin. The amount is 5 to 0.01 parts by weight, preferably 4 to 0.02 parts by weight, and more preferably 3 to 0.03 parts by weight with respect to the total amount of 100 parts by weight.

  Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. Carbon black having an oil absorption of 50 to 400 cm 3/100 g is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treatment agent.

  Further, as the titanium oxide, titanium oxide having a rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, the thermoplastic resin is preferably a polyester resin such as a polylactic acid resin, and a polylactic acid resin is particularly preferably used.

  For the resin composition of the present invention, a stabilizer (hindered phenol-based antioxidant, phosphorus-based antioxidant, amine-based antioxidant, sulfur-based antioxidant, as long as the object of the present invention is not impaired. Light stabilizers, UV absorbers, copper damage inhibitors, etc.), mold release agents (fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partial saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, Aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone) and the like can be added as necessary.

  Although it does not specifically limit about the manufacturing method of the resin composition of this invention, For example, 1 or more types of resin chosen from (A) polylactic acid resin and (B) cellulose ester, (C) aromatic polycarbonate resin, ( D) Pre-blending compatibilizer and other additives such as (E) flame retardant as required, (A) Melt uniformly using a single or twin screw extruder above the melting point of polylactic acid resin Kneading method.

  In addition, the resin composition of the present invention in which (A) a flame retardant is blended with (A) a polylactic acid resin and (B) one or more resins selected from cellulose esters, (C) an aromatic polycarbonate resin, and (D) a compatibilizer. The product is a molded product having a flame retardance of 1.6 mm (1/16 inch) thickness according to the UL standard, and can give performances of V-2, V-1, V-0, 5V. Can provide performance of V-1, V-0, 5V, and in a more preferred embodiment, performance of V-0, 5V can be provided.

  The resin composition of the present invention is a composition having unique characteristics, and various methods are employed by methods such as extrusion molding, injection molding, blow molding, and spinning into various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn. It can be processed into product shapes and used, especially as mechanical parts, electrical / electronic parts, automobile parts, optical equipment, building components and daily products, especially mechanical parts, electrical parts -It is preferably used as a molded product of electronic parts and automobile parts.

  Examples of the extrusion-molded product obtained by the above-described extrusion molding include extrusion-molded products such as films, inflation films, sheets, tubes and round bars, and can be used after being stretched. Further, it can be further processed into a molded product for various uses such as electric / electronic parts, automobile parts, optical equipment, building materials and daily necessities. In addition, examples of the mechanical mechanism parts of injection molded products obtained by injection molding include various types of bearings such as cleaning jigs, oilless bearings, stern bearings, underwater bearings, motor parts, lighters, typewriters, etc. As electrical and electronic parts of injection molded products, electrical equipment housing, OA equipment housing, various covers, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, Capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, breaker, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage , FDD chassis, motor Rush holder, parabolic antenna, CD tray, cartridge, cassette, sorter, AC adapter, charging stand, switchboard, outlet cover, VTR parts, TV parts, iron, hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio / audio Examples of moldings that make up part of laser discs, compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, etc. It can also be used as injection-molded automotive parts such as precision machine parts, alternator terminals, alternator connectors, IC regulators, exhaust gas valves, and other fuel-related / exhaust / intake valves. Various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position Sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire Harness, window washer nozzle, air conditioner panel switch board, fuel related It constitutes more than a part of electromagnetic valve coil, fuse connector, horn terminal, electrical parts insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, etc. Examples of the optical device of the injection molded product include a molded product that constitutes a part of a microscope, binoculars, a camera, a watch, and the like. In addition, blow molded products are molded into the necessary shape as bellows, boots, bottles, and different diameter pipes / cylinders, such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building components, and daily necessities. It can be used for various purposes as a molded product.

  The present invention will be described in more detail below by way of examples, but these examples do not limit the present invention.

[Examples 1 to 77 , Comparative examples 1 to 27 ]
(A) Poly-L lactic acid resin having a D-form content of 1.2% and a PMMA equivalent weight average molecular weight of 160,000, cellulose ester, aromatic polycarbonate resin, compatibilizer, and various flame retardants shown below , Fluorine-based resin, epoxy compound, alkaline earth metal salt, other resin, reinforcing material, layered silicate, plasticizer, and other stabilizers are mixed in the proportions shown in Tables 1 to 6, respectively, Using a twin-screw extruder, melt kneading was performed under conditions of a cylinder temperature of 250 ° C. and a rotation speed of 150 rpm, a molten gut was drawn from the die in a strand shape, water-cooled with a cooling bath, and a resin composition pelletized with a strand cutter was obtained. .

In Tables 1 to 8, (B) cellulose ester, (C) aromatic polycarbonate resin, (D) compatibilizer, (E) various flame retardants, (F) fluororesin, (G) epoxy compound, ( The symbols of L) alkaline earth metal salt, (H) other resin, (I) fiber reinforcement, (J) layered silicate, (K) plasticizer, (L) other additives indicate the following contents: ("-/-" Represents copolymerization or graft copolymerization, and "-g-" represents graft copolymerization; the same applies hereinafter). In addition, the compounding quantity of (D)-(L) component is a compounding with respect to 100 weight part of total amounts of 1 or more types of resin chosen from (A) polylactic acid resin and (B) cellulose ester, and (C) aromatic polycarbonate resin. Amount.
B-1: (B) Cellulose acetate propionate ("CAP" manufactured by Eastman Chemical Co., acetate substitution degree 0.1, propionate substitution degree 2.93).
B-2: (B) Cellulose diacetate (“LT-40” manufactured by Daicel Chemical Industries, Ltd., acetate substitution degree 2.42).
B-3: (B) Cellulose triacetate (“LT-35” manufactured by Daicel Chemical Industries, Ltd., acetate substitution degree 2.93).
C-1: (C) aromatic polycarbonate resin (“A-1900” manufactured by Idemitsu Petrochemical Co., Ltd.)
D-1: (D) talc (“P-6” manufactured by Nippon Talc Co., Ltd., average particle size of about 4 μm).
D-2: (D) talc (“MS-P” manufactured by Nippon Talc Co., Ltd., average particle diameter of about 12 μm).
D-3: (D) Poly (ethylene / ethyl acrylate / maleic anhydride) -g-polymethyl methacrylate (“Modiper” A-8200, manufactured by NOF Corporation).
D-4: (D) ethylene / glycidyl methacrylate-g-polymethyl methacrylate (“Modiper” A-4200 manufactured by NOF Corporation).
D-5: (D) Aromatic polycarbonate resin-g-AS resin (Nippon Yushi Co., Ltd. product "Modiper" C-L430D).
D-6: (D) Aromatic polycarbonate resin-g-maleic anhydride / AS resin (manufactured by NOF Corporation “Modiper” C-L440-G).
D-7: (D) Ethylene / glycidyl methacrylate (“Bond First” 2C, manufactured by Sumitomo Chemical Co., Ltd.).
D-8: (D) ethylene / methyl acrylate / glycidyl methacrylate (“bond first” 7M manufactured by Sumitomo Chemical Co., Ltd.).
D-9: (D) Ethylene / ethyl acrylate / maleic anhydride (“Bondyne” HX8290, manufactured by Sumitomo Chemical Co., Ltd.).
D-10: (D) Styrene / ethylene / butadiene / maleic anhydride (“Tufprene” M1943 manufactured by Asahi Kasei Kogyo Co., Ltd.).
D-11: (D) polyethylene / maleic anhydride wax (“Mitsui High Wax” 1105A manufactured by Mitsui Chemicals, Inc.).
D-12: (D) Polypropylene / maleic anhydride wax (“Mitsui High Wax” NP0555A manufactured by Mitsui Chemicals, Inc.).
D-13: (D) Organoaluminum compound (Ajinomoto Fine Techno Co., Ltd. “Plenact” AL-M).
E-1: condensed phosphate ester (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.).
E-2: Triphenyl phosphate (“TPP” manufactured by Daihachi Chemical Industry Co., Ltd.).
E-3: Melamine cyanurate (“MC-440” manufactured by Nissan Chemical Industries, Ltd.).
E-4: Ammonium polyphosphate (“Fire Cut” FCP730, manufactured by Suzuhiro Chemical Co., Ltd.).
E-5: Melamine polyphosphate (“Melpua” 200 manufactured by DSM).
E-6: Zinc borate ("Firebreak" ZB manufactured by Borax).
F-1: Tetrafluoroethylene (“Teflon (registered trademark)” 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.).
F-2: Acrylic modified tetrafluoroethylene ("Maybrene (registered trademark)" A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).
G-1: Versatic acid glycidyl ester (“Cajura E10” manufactured by Japan Epoxy Resin Co., Ltd.).
G-2: Bisphenol A diglycidyl ether (“Epicoat” 828, manufactured by Japan Epoxy Resin).
H-1: Nylon 6 resin (“Amilan” CM1010 manufactured by Toray Industries, Inc.).
H-2: Polybutylene (terephthalate / adipate) resin ("Ecoflex" manufactured by BASF).
H-3: Silicone / acrylic composite core-shell rubber ("METABRENE" SX-005 manufactured by Mitsubishi Rayon Co., Ltd.).
H-4: Polyester elastomer resin (“Hytrel” 4057 manufactured by Toray DuPont Co., Ltd.).
H-5: AS resin (styrene / acrylonitrile = 74/26, manufactured by Toray Industries, Inc.).
H-6: Polybutylene terephthalate ("Toraycon" 1401X31 manufactured by Toray Industries, Inc.).
H-7: Polytrimethylene terephthalate resin ("Cortina" manufactured by Shell).
H-8: Polyethylene (terephthalate / succinate) resin ("Biomax" manufactured by DuPont).
H-9: Nylon 6 / polyethylene glycol resin (“Pelestat” manufactured by Sanyo Chemical Industries, Ltd.).
H-10: Polybutylene succinate resin (“Bionore” 1001 manufactured by Showa Polymer).
H-11: Polymethyl methacrylate resin (“SUMIPEX” LG35 manufactured by Sumitomo Chemical).
H-12: Polycaprolactone resin (“Placcel” H7 manufactured by Daicel Chemical Industries, Ltd.).
H-13: Ionomer (“High Milan” 1555 manufactured by Mitsui & DuPont Polychemical Co., Ltd., alkali metal salt is sodium ion).
H-14: Ionomer (“High Milan” 1706, manufactured by Mitsui DuPont Polychemical Co., Ltd., alkali metal salt is zinc ion).
H-15: Styrene / ethylene / butadiene / styrene (“Clayton” 1650 manufactured by Shell Chemical Co., Ltd.).
H-16: Styrene / butadiene / styrene / epoxy (“Epofriend” A1010 manufactured by Daicel Chemical Industries, Ltd.).
I-1: Glass fiber of chopped strand (CS-3J948 manufactured by Nitto Boseki Co., Ltd.).
J-1: Organized layered silicate (“MTE” manufactured by Corp Chemical Co., Ltd.).
K-1: Ethylene bis lauric acid amide ("Slipax" L manufactured by NOF Corporation).
K-2: Polyethylene propylene glycol ("Pluronic" F68 manufactured by Asahi Denka Kogyo Co., Ltd.).
L-1 (alkaline earth metal salt): Calcium carbonate (“KSS1000” manufactured by Dowa Calfine Co., Ltd.).
L-2 (hindered phenol-based antioxidant): pentaerythrityl-tetrakis {3- (3,5-t-butyl-4-hydroxyphenyl) propionate} ("Irganox" 1010 manufactured by Ciba Geigy Japan, Inc.) . Further, the obtained resin composition was subjected to injection molding at a cylinder temperature of 240 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. to obtain various molded products. ) To (6) to evaluate the characteristics.

(1) Whiteness Using a SM color computer manufactured by Suga Test Instruments Co., Ltd., model SM-3, the YI value (yellowness) of the molded product was measured. The YI value is a measured value that is preferably used for white to yellow color determination with white as a standard. The larger the YI value, the closer to yellow, and the smaller the YI value, the closer to white.

(2) Impact strength An Izod impact test (no notch) was measured according to ASTM method D256 using a 3 mm-thick impact test piece produced by injection molding.

(3) Surface appearance (compatible)
The surface appearance of a square plate having a thickness of 80 mm × 80 mm × 3 mm produced by injection molding was visually observed, and the presence or absence of pearly luster, surface peeling and flow mark and the degree thereof were evaluated according to the following guidelines. This evaluation can also be used as an index for judging the compatibility of the resin composition. Moreover, the resin composition which is inferior in compatibility, has a large ballast effect, and has not been able to draw a strand is determined as the following xx, and the evaluation proceeds to (1), (2), (4), (5) and (6). I could not do it.
A: There is no pearly luster, no surface peeling and no flow mark, and the indoor fluorescent lamp line looks clear.
○: Although there is no pearly luster, surface peeling or flow mark, the indoor fluorescent lamp line looks unclear. (Triangle | delta): Although pearl luster and surface peeling do not generate | occur | produce, a flow mark is recognized.
X: Nacreous or surface peeling is recognized.
XX: No pellets were obtained due to the ballast effect during melt kneading.

(4) Flame retardance Using test pieces of 127 mm x 12.7 mm x 0.8 mm (5 inches x 1/2 inches x 1/32 inches) produced by injection molding, an American UL standard subject 94 (UL94) Combustion test is performed in accordance with the vertical combustion test method, flame retardancy is evaluated, and the evaluation rank is indicated by V-0, V-1, V-2 in the order of excellent flame retardancy, and corresponds to the above rank The thing which did not do was made out of specification.

(5) Hydrolyzability A 3 mm-thick ASTM No. 1 dumbbell test piece prepared by injection molding was put into a constant temperature and high humidity container of “Humidi Cabinet” LHL-112 manufactured by Tabay Espec. The conditions of the temperature and humidity of the constant temperature and high humidity and the treatment time are 60 ° C. × 95% RH × 200 h, a tensile test is performed according to ASTM method D638, the tensile strength retention is obtained from the following formula, and hydrolyzability is obtained. It was used as an index.
Tensile strength retention rate (%) = (Tensile strength after treatment ÷ Tensile strength of untreated product) × 100

(6) Thermal deformation temperature A thermal deformation test was performed under a load condition of 1.82 MPa according to ASTM method D648 using a 3 mm-thick test piece produced by injection molding.

  These results are also shown in Tables 1 to 8.

Examples 1-12 in Table 1, (A) a resin composition containing a ~ (D) component of the present invention can be said whiteness, impact strength, and a molded article comprising a resin composition having excellent surface appearance.

From the comparison between Example 1 and Comparative Example 1 , it was found that the use of an inorganic filler having an average particle size of 10 μm or less as the compatibilizer of component (D) is more white than the inorganic filler having an average particle size exceeding 10 μm. And the impact strength was excellent.

From Comparative Examples 2-4 of Table 2, the resin composition which does not mix | blend the compatibilizer of (D) component was inferior in compatibility, the ballast effect was large, and the strand was not drawn, and the pellet was not obtained.

From Comparative Examples 5-7 of Table 2, the resin composition which does not mix | blend the aromatic polycarbonate resin of (C) component was a resin composition inferior in whiteness, impact strength, and surface appearance.

Comparative Examples 8 to 19 in Table 2 are resin compositions containing other thermoplastic resins in place of the aromatic polycarbonate resin of component (C), but all were inferior in whiteness and surface appearance. However, there was a resin composition with improved performance in terms of impact strength.

From Examples 13-15 of Table 3, even if it is a resin composition close | similar to the minimum and upper limit of the compatibilizer compounding quantity of (D) component, it consists of a resin composition excellent in whiteness, impact strength, and surface appearance. It can be said to be a molded product.

In the case of a resin composition in which the amount of component (C) or component (D) shown in Comparative Examples 23 to 27 in Table 3 is not within the scope of the present invention, any one of whiteness, impact strength, surface appearance, or a plurality of performances It was a resin composition inferior to.

Examples 16 to 27 in Table 4 are resin compositions further blended with (E) a flame retardant, and are molded products imparted with flame retardancy while maintaining the performance of whiteness, impact strength, and surface appearance. I can say that.

In particular, from Example 16 , the material using the specific condensed phosphate ester obtained excellent flame retardancy with a small blending amount.

Further, from Examples 22 to 23 , the material further blended with (F) fluorine-based resin does not show drip at the time of combustion, exhibits a higher flame retardancy V-0, and has the effect of modifying the flame retardancy. It can be said that there is.

Further, from Examples 24-27 , the material further blended with (G) epoxy compound is excellent in hydrolyzability while maintaining the performance and flame retardancy of the present invention, and is an alkaline earth metal salt or hindered phenol-based oxidation. The material combined with the inhibitor showed a higher degree of hydrolyzability.

Examples 28 to 32 in Table 5 are resin compositions obtained by mixing at least one of (I) glass fiber, (J) organically modified layered silicate, and (K) plasticizer in Example 16 of Table 4. maintaining the performance and flame retardancy of the inventions can be said that the effect of modifying et thermal deformation temperature. In particular, the glass fiber (I) had a high effect of modifying the heat distortion temperature.

Examples 33 to 44 in Table 5 are resin compositions obtained by blending (H) other resins with Example 16 in Table 4 and maintain any flame retardancy while maintaining whiteness, impact strength, or heat distortion temperature. The effect of improving the performance can be said from the comparison with Example 16 in Table 4.

Examples 45 to 55 in Table 6 are resin compositions using different types of flame retardants in combination, and compositions using fluorine resins together, and epoxy compounds, other resins, glass fibers, organic layered silicates, plasticizers, It is a resin composition containing other stabilizers in combination, and high flame retardancy can be obtained while maintaining the performance of the present invention. Furthermore, it can be said that a molded article having excellent hydrolyzability and heat distortion temperature can be obtained.

Examples 56 to 60 in Table 7 are compositions using the component (D) different from Example 8 although the blending amounts are the same as those in Example 8, and as in Example 8, whiteness and impact strength. It can be said that it is a molded article made of a resin composition having an excellent surface appearance.

Examples in Table 8 61-71, said an embodiment 56 to 60 included in the (D) a composition component quantity was further compounded, whiteness, impact strength, excellent surface appearance, particularly from Example 8 It can be said that it is a molded article made of a resin composition having excellent impact strength. Examples 72 to 73 are compositions in which the mixing ratio of (A) polylactic acid and (C) aromatic polycarbonate resin was changed with respect to the composition of Example 62 , but whiteness, impact strength, surface It can be said that it is a molded article made of a resin composition having an excellent appearance.

Examples 74 to 77 in Table 8 are compositions in which the composition of Example 8 is blended with (H) an ionomer of another resin or a styrene resin, and is excellent in whiteness, impact strength, and surface appearance. 8 can be said to be a molded article made of a resin composition having an excellent impact strength.

Claims (11)

One or more resins selected from (A) polylactic acid resin and (B) cellulose ester, 75 to 10% by weight, (C) aromatic polycarbonate resin from 25 to 90% by weight, and at least selected from (a) and (b) below one (D) a compatibilizing agent (a) and (B) with one or more selected from (C) the total amount resin composition obtained by blending 1 to 50 parts by weight per 100 parts by weight of component (although (C) Composition ratio (B parts by weight) of polylactic acid resin per 100 parts by weight of aromatic polycarbonate resin and (a) Composition ratio (C parts by weight) of talc with an average particle size of 5 μm or less Excludes aromatic polycarbonate resin composition in a range satisfying (I)
0.3 × B ≦ C (I)) .
(B) grafting the average particle size of 5μm or less of talc (B) an acid anhydride or copolymerizing ethylene copolymer (B) the cellulose ester, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, claim 1 is at least one cellulose ester selected from the group consisting of cellulose acetate phthalate Resin composition. Further, (E) one or more flame retardants selected from brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants are blended. 3. The resin composition according to any one of 2 above. The resin composition according to claim 3 , wherein the phosphorus-based flame retardant (E) is a phosphate ester. Furthermore, the resin composition of any one of Claims 1-4 formed by mix | blending (F) fluorine-type resin. Furthermore, the resin composition of any one of Claims 1-5 formed by mix | blending (G) an epoxy compound. Further, (H) (A) polylactic acid resin, (B) cellulose ester, (C) polycarbonate resin and (F) polyester resin which is a thermoplastic resin other than fluororesin , polyamide resin, styrene resin, and silicone compound The resin composition according to any one of claims 1 to 6 , comprising one or more thermoplastic resins selected from core-shell rubber . Furthermore (I) the resin composition according to any one of claims 1 to 7, by blending the fibrous reinforcement. Furthermore, the resin composition of any one of Claims 1-8 formed by mix | blending (J) layered silicate. Further (K) resin composition according to any one of claims 1 to 9, by blending a plasticizer. Molded article comprising a resin composition according to any one of claims 1-10.