JP2007126630A - Functional filler and resin composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional filler having excellent dispersibility or interaction in an aliphatic polyester such as polylactic acid which is a matrix polymer and excellent improving effects on heat resistance, moldability or mechanical strength of the aliphatic polyester such as the polylactic acid and to provide a resin composition comprising the functional filler. <P>SOLUTION: The functional filler is obtained by chemically and/or physically modifying the surface or ends of a filler to be a raw material with the polylactic acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a functional filler and a functional filler composition containing the functional filler, a resin composition containing the functional filler, a production method thereof, and a molded article made of the resin composition.

  Polylactic acid is a kind of biodegradable polymer, and the raw material is a recyclable plant resource, a food residue of daily life, waste paper, etc., and can be produced without using petroleum resources. In addition, since waste decomposes in nature, waste disposal is unlikely to be a problem like conventional plastic products. Therefore, polylactic acid is expected to play a major role in solving problems of resources, energy, and the environment from now to the future.

  Specifically, when used as an agricultural material, it is not necessary to collect it after use. Moreover, when it is used for a convenience store lunch or a food packaging container, it is possible to throw away food waste as it is without separating the leftover food or food after use. Therefore, it is possible to rationalize the material cycle and logistics that make use of the characteristics of plant-derived biodegradable resins, which can greatly contribute to labor saving and energy saving. Furthermore, even when used in vivo, the degradation product of polylactic acid is lactic acid, carbon dioxide, and water that are harmless to the human body, and is therefore used for medical materials.

  However, polylactic acid is excellent in transparency like PS and PET resins, but has a problem that it is inferior in mechanical strength such as heat resistance, moldability and impact resistance. Such a property is a problem in developing a wide range of applications.

In order to improve the mechanical strength of polylactic acid such as heat resistance, moldability and impact resistance, a method of blending a filler such as silica with polylactic acid has been attempted (see Patent Documents 1 to 3).
JP 2005-200600 A JP 2005-112456 A JP 2004-224990 A

  However, conventionally used fillers such as silica are insufficient in dispersibility in polylactic acid as a matrix polymer and interaction with polylactic acid. Therefore, even if these fillers are blended with polylactic acid, the mechanical strength such as heat resistance, moldability and impact resistance has not been improved so as to withstand practical requirements.

  Therefore, the problem to be solved by the present invention is a functional filler which is excellent in dispersibility in polylactic acid which is a matrix polymer and interaction with polylactic acid, and is excellent in the effect of improving the heat resistance, moldability and mechanical strength of polylactic acid. And providing a functional filler composition and a resin composition containing the functional filler. Another object of the present invention is to provide a method for producing these functional fillers and a molded product comprising the above resin composition.

  In order to solve the above-mentioned problems, the present inventors have made intensive studies on fillers added to a polylactic acid composition. As a result, an optically active lactic acid oligomer or polymer such as poly-D-lactic acid is a matrix polymer using the property of strongly interacting with an oligomer or polymer of lactic acid which is an optical isomer such as poly-L-lactic acid. It has been found that the above problem can be solved by modifying the filler with a substituent that interacts with the molecule. More specifically, such a functional filler interacts with a plurality of polylactic acid molecules, so to speak, has the effect of cross-linking a plurality of polylactic acid molecules, thereby improving the heat resistance and strength of polylactic acid. Can do.

  The functional filler of the present invention comprises a raw material filler and polylactic acid, and the surface or the end of the raw material filler is modified with polylactic acid.

  In the functional filler, the raw material filler preferably has a functional group that can be chemically and / or physically bonded to a carboxyl group, a hydroxyl group, or a carbonyl group on the surface or terminal thereof. Such raw material filler is easy to introduce polylactic acid. The raw material filler includes inorganic fillers such as silica particles and organic fillers such as polyalcohol.

  As said functional filler, the polylactic acid which has modified the surface or terminal of the raw material filler is poly D-lactic acid or poly L-lactic acid. Since such a functional filler strongly interacts with the optical isomer of the polylactic acid, that is, poly L-lactic acid or poly D-lactic acid, the heat resistance of the material using poly L-lactic acid or poly D-lactic acid as a matrix polymer, etc. Can be remarkably improved.

  The functional filler composition of this invention contains the said functional filler and the unbonded polylactic acid produced | generated at the time of the said functional filler manufacture. Such a resin composition is advantageous from the viewpoint of cost because it can be produced by omitting the purification step.

Moreover, the resin composition of the present invention comprises:
Including the functional filler and polylactic acid which is a matrix polymer,
It is characterized in that at least a part of the polylactic acid interacts with the polylactic acid modifying the surface or terminal of the functional filler.

  Examples of the resin composition further include unbound polylactic acid produced during the production of the functional filler.

  As the resin composition, the polylactic acid that modifies the surface or terminal of the functional filler is composed of D-lactic acid or L-lactic acid, and the polylactic acid that is a matrix polymer is composed of optical isomers of the D-lactic acid or L-lactic acid. Those are preferred. In addition, it is also preferable that the unbonded polylactic acid produced during the production of the functional filler is composed of D-lactic acid or L-lactic acid, and the polylactic acid that is a matrix polymer is composed of the optical isomer of D-lactic acid or L-lactic acid. In such a composition material, since the functional filler and the polylactic acid in the matrix polymer are strongly interacting with each other, the heat resistance and the like are further improved.

The method for producing a functional filler according to the present invention is as follows.
A step of mixing a solution of lactic acid and / or lactide, or a melt of lactic acid and / or lactide and a raw material filler; and polymerizing the lactic acid and / or lactide, so that the surface or terminal of the raw material filler is made of polylactic acid. It includes a step of modifying.

  Moreover, when manufacturing the functional filler composition containing the unbonded polylactic acid produced | generated at the time of functional filler manufacture, what is necessary is just to use an excess amount of lactic acid and / or lactide with respect to a raw material filler in the said manufacturing method. .

The method for producing a resin composition according to the present invention includes:
Mixing a raw material filler with a solution of lactic acid and / or lactide or a melt of lactic acid and / or lactide;
A step of polymerizing lactic acid and / or lactide to modify the surface or terminal of the raw material filler with polylactic acid to form a functional filler; and the functional filler is polylactic acid which is a matrix polymer, and at least one of them And a step of mixing with a part that interacts with polylactic acid that modifies the surface or terminal of the functional filler.

  The molded product of the present invention comprises the above resin composition.

  According to the present invention, the following effects can be obtained. That is, by modifying the filler surface with polylactic acid that interacts with the matrix polymer polylactic acid, the dispersibility of the filler in the matrix polymer is greatly improved. Moreover, when the polylactic acid on the filler surface and the matrix polymer form a stereocomplex, the heat resistance and strength of the resulting resin composition are improved. Furthermore, since the stereo complex functions as a crystal nucleating agent, the crystallization speed of the resin composition can be increased, the molding speed, the stretching temperature and the stretching ratio can be improved, and the physical properties and moldability of the resulting molded product can be improved. Improvements can be made and applications can be expanded. Moreover, since the obtained molded object is reinforced with the filler, the strength is high. Due to the properties of the functional filler of the present invention described above, when the resin composition of the present invention is processed in a solid state or in a molten state such as stretching or molding, the crystal size is small, the filler effect, the melt viscosity It is possible to perform uniform stretching and molding due to the fact that it is high, etc., and it is possible to improve the stability during production of stretched products and molded products, and the quality and performance of products.

  The functional filler of the present invention comprises a raw material filler and polylactic acid, and the surface or the end of the raw material filler is modified with polylactic acid. The schematic diagram which shows the outline | summary of the functional filler of this invention in FIG. 1 is shown. In the following, polylactic acid that modifies the surface or end of the filler may be referred to as “polylactic acid (A)”.

  Conventionally, silica, which is widely used as a filler for polylactic acid, is compatible with polylactic acid by modifying the surface of silica with a silane coupling agent in order to increase dispersibility in aliphatic polyester such as polylactic acid. A method is used to increase the value. However, the effect was not sufficient. On the other hand, in the present invention, by introducing polylactic acid which is much more compatible with polylactic acid than the silane coupling agent on the surface of the filler, the dispersibility or interaction in polylactic acid is extremely high. can do.

  More specifically, optically active lactic acid oligomers and polymers such as poly-D-lactic acid strongly interact with lactic acid oligomers and polymers that are optical isomers such as poly-L-lactic acid. Therefore, for example, if a mixture of poly-D-lactic acid and poly-L-lactic acid is used as the matrix polymer, the matrix polymers interact with each other, so that the heat resistance of the polylactic acid composition material is considered to be improved. However, in such an embodiment, for example, one poly D-lactic acid has a high probability of interacting with one poly L-lactic acid, and one poly D-lactic acid has a very low probability of interacting with two or more poly L-lactic acids. Conceivable. On the other hand, the functional filler of the present invention can be combined with a plurality of matrix polymer molecules depending on the number of polylactic acids bonded to the surface or the end of the filler, thereby forming a stereocomplex. As a result, the heat resistance and the like of the polylactic acid composition material can be significantly improved.

  The polylactic acid (A) may be selected so that at least a part thereof interacts with the matrix polymer molecule to which the functional filler is added. For example, when the matrix polymer molecule is poly-D-lactic acid, at least a part thereof has an oligomer or polymer part made of L-lactic acid, and preferably poly-L-lactic acid mainly composed of L-lactic acid. Is used. In addition, when the block made of D-lactic acid is X and the block made of L-lactic acid is Y, when the polylactic acid that is a matrix polymer is a block copolymer that is XYX, Lactic acid (A) is a YXY block copolymer. Furthermore, when polylactic acid which is a matrix polymer is, for example, a mixture of poly D-lactic acid and poly L-lactic acid, polylactic acid (A) may be a mixture of poly D-lactic acid and poly L-lactic acid. The polylactic acid (A) may be a random copolymer of D-lactic acid and L-lactic acid as long as at least a part of the matrix polymer molecule can interact with the matrix polymer molecule. In any case, polylactic acid (A) can be appropriately selected according to the optical properties of the matrix polymer.

  In the present invention, “poly-D-lactic acid” and “poly-L-lactic acid” are not limited to those composed only of D-lactic acid or L-lactic acid, respectively, and mainly comprise D-lactic acid or L-lactic acid, respectively. Anything is acceptable. Here, “mainly” means that 80% by mass or more of lactic acid constituting “poly D-lactic acid” or “poly L-lactic acid” is preferably D-lactic acid or L-lactic acid, respectively. Preferably 85% by weight or more, more preferably 90% by weight or more is D-lactic acid or L-lactic acid, respectively. Components other than D-lactic acid or L-lactic acid in poly-D-lactic acid or poly-L-lactic acid may be their respective optical isomers, that is, poly-D-lactic acid may be L-lactic acid, and can be polymerized into lactic acid. Other components may be used. Examples of other components polymerizable to lactic acid include dihydric or higher alcoholic compounds or divalent or higher carboxylic acid compounds, or compounds capable of ring-opening polymerization such as cyclic lactones, cyclic ethers, and cyclic lactams. be able to.

  Polylactic acid has high crystallinity when the ratio of L-lactic acid or D-lactic acid is high, that is, high optical purity, and is excellent in heat resistance and mechanical properties. On the other hand, a copolymer having a relatively high ratio of L-lactic acid in poly-D-lactic acid or a ratio of D-lactic acid in poly-L-lactic acid is low in crystallinity or amorphous, and has low heat resistance, In addition, mechanical properties are low. Therefore, polylactic acid with high optical purity is suitable as the polylactic acid of the present invention.

  The polylactic acid (A) preferably has a number average molecular weight of 1 to 1,000,000. If molecular weight is 100 or more, the dispersibility in the matrix polymer of the functional filler concerning this invention can fully be ensured. On the other hand, if the molecular weight is 1 million or less, a stereocomplex can be sufficiently formed. In addition, the measurement of the number average molecular weight of polylactic acid (A) can be performed using GPC (gel permeation chromatography) measurement as mentioned later.

  In the functional filler according to the present invention, the surface or terminal of the raw material filler is modified with polylactic acid (A). This modification is performed by chemically and / or physically binding polylactic acid (A) to the surface or terminal of the raw material filler. Here, examples of the chemical bond include an ester bond formed with a hydroxyl group of a terminal lactic acid molecule of polylactic acid, an ester bond formed with a carboxyl group of a terminal lactic acid molecule, and an amide bond. Examples of physical bonds include ionic bonds and hydrogen bonds. Therefore, if the raw material filler has a functional group that can be chemically and / or physically bonded to a carboxyl group, a hydroxyl group or a carbonyl group on the surface or terminal, it can be easily modified with polylactic acid (A). Examples of such functional groups include hydrophilic functional groups such as amino groups, hydroxyl groups, carboxyl groups, and epoxy groups. When the raw material filler does not have these hydrophilic functional groups on the surface or terminal thereof, these hydrophilic functional groups may be introduced using a known method.

  The raw material filler may be any of inorganic rod fillers, layer fillers, particulate fillers, and sol solutions thereof, and an organic compound (organic filler) that dissolves or disperses uniformly with the polymer matrix is also used. Is possible. Metal alkoxides that are raw materials for inorganic fillers can also be used.

  As the rod-like filler, that is, the fibrous filler or the needle-like filler, those having the highest aspect ratio (length / diameter or diameter / thickness) and capable of greatly improving the mechanical properties of the resin composition are suitable. is there. Specific examples thereof include glass fiber, asbestos fiber, carbon fiber (including fiber such as carbon nanotube, spherical new carbon such as needle or fullerene), graphite fiber, metal fiber, rod-like hydroxyapatite, potassium titanate whisker. , Aluminum borate whisker, Magnesium whisker, Silicon whisker, Wollastonite, Sepiolite, Asbestos, Slag fiber, Zonolite, Elestadite, Boehmite, Gypsum fiber, Silica fiber, Alumina fiber, Silica / alumina fiber, Zirconia fiber, Boron nitride Inorganic and needle-like fillers such as fiber and boron fiber; polyester fiber, nylon fiber, acrylic fiber, cellulose fiber, acetate fiber, aramid fiber, kenaf fiber, ramie, cotton, jute, hemp, sisal, sub , Linen, silk, abaca, wood pulp, waste paper, and organic fibrous fillers such as wool.

  Although the layered or plate-like filler is inferior in impact strength to the particulate filler, it has an aspect ratio higher than that of the granular filler, and therefore has advantages such as a large effect of improving rigidity and excellent dimensional stability. is doing. Specifically, natural and synthetic smectites, etc., specifically clays such as Kunipia P and smecton made by Kunimine Industries, Ltd .; plate-like alumina, talc, mica, sericite, glass flakes, various metal foils, graphite, plate-like Examples thereof include calcium carbonate, plate-like aluminum hydroxide, plate-like magnesium hydroxide and the like.

  A spherical or irregular shaped particulate filler is a filler having an aspect ratio close to 1. Specific examples thereof include hydroxyapatite, calcium carbonate, silica, mesoporous silica, zirconia, alumina, Y-PSZ, spinel, talc, mullite, cordierite, silicon carbide, aluminum nitride, hematite, cobalt blue, cobalt violet, cobalt Green, magnetite, Mn-Zn ferrite, Ni-Zn ferrite, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, zinc oxide, titanium oxide, magnesium fluoride, tin oxide , Antimony-containing tin oxide (ATO), tin-containing indium oxide, barium titanate, PT, PZT, PLZT, clay materials, various ore pulverized products, various beads, various balloons, etc. That.

  Examples of the sol solution include silica sol solution and boehmite sol solution manufactured by Nissan Chemical Co., Ltd., Fuso Chemical Co., Ltd. and Kawaken Fine Chemical Co., Ltd.

  Examples of metal alkoxides include silicon-based alkoxides, titanium-based alkoxides, aluminum-based alkoxides, zirconium-based alkoxides, tin-based alkoxides, germanium-based alkoxides, rare earth-based alkoxides, and mixtures and / or composite alkoxides. Can be mentioned.

  Examples of silicon-based alkoxides include tetraethoxysilane and the like, tetraalkoxysilane having 1 to 5 carbon atoms in the alkoxy group; methyltriethoxysilane and the like, methyltrialkoxysilane; phenyltriethoxysilane and the like, phenyltrialkoxysilane; Ethoxysilane, etc. Dimethyldialkoxysilane; Diphenyldimethoxysilane, Diphenylsilanediol, etc. Diphenyl dialkoxysilane; Chisso Corporation Silaace S210 and S220, Vinyltrialkoxysilane; Chisso Corporation Silaace S310, etc. (2-aminoethyl) 3-aminopropylmethyl dialkoxysilane; N- (2-aminoethyl) 3-aminopropyltria, such as Silaace S320 manufactured by Chisso Corporation Coxysilane; Chisso Corporation Silaace S330 and S360, etc., 3-aminopropyltrialkoxysilane; Chisso Corporation Silaace S510, etc., 3-glycidoxypropyltrialkoxysilane; Chisso Corporation Silaace S520, etc. 3 -Glycidoxypropylmethyl dialkoxysilane; Silaace S530 manufactured by Chisso Corporation, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane; Silaace S610 manufactured by Chisso Corporation, 3-chloropropylmethyl Dialkoxysilane; 3-Cyclopropyltrialkoxysilane, such as Silaace S620 manufactured by Chisso Corporation; 3-methacryloxypropyltrialkoxysilane, such as Silaace S710 manufactured by Chisso Corporation N- (1,3-dimethylbutylidene) -3- (trialkoxysilyl) -1-propanamine, such as Silaace S810 manufactured by Chisso Corporation, 3-mercaptopropyltrialkoxysilane, such as Silacace S340 manufactured by Chisso Corporation N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrialkoxysilane / hydrochloride, such as Silaace S350, manufactured by Chisso Corporation; N, N′-bis [, such as Silaace XS1003, manufactured by Chisso Corporation; 3- (trialkoxysilyl) propyl] ethylenediamine; oligomers of amino-based silane coupling agents, such as Silaace oligomers MS3201, MS3202, MS3301, and MS3302 manufactured by Chisso Corporation; Silacace oligomers MS5101 and M manufactured by Chisso Corporation Epoxy silane coupling agent oligomer such as 5102; Silaplane FM-1111 manufactured by Chisso Corporation, Silaplane FM-1211, Silaplane FM-1125, etc .; Terminal hydrogenated polydimethylsiloxane; Silaplane manufactured by Chisso Corporation Terminal vinylated polydimethylsiloxane such as FM-2231; Silaplane FM-7711, Silaplane FM-7721, Silaplane FM-7725, Silaplane FM-0711, Silaplane FM-0721, Silaplane FM manufactured by Chisso Corporation --0725, Silaplane TM-0701, Silaplane TM-0701T, etc., terminal methacryloxy-based polydimethylpolysiloxane; Chisso Corporation Silaplane FM-0411, Silapre FM-0421, Silaplane FM-0425, Silaplane DA-11, Silaplane DA-21, Silaplane DA-25, etc., terminal polydimethylsiloxane hydroxide; Chisso Corporation Silaplane FM-0511, Silaplane Terminal epoxidized polydimethylsiloxane such as FM-0521, Silaplane FM-0525; terminal carboxylated polydimethylsiloxane such as Silaplane FM-0611, Silaplane FM-0621, Silaplane FM-0625 manufactured by Chisso Corporation; Poly Methyl silsesquioxane 100% methyl, polymethyl-hydridosilsesquioxane 90% methyl, 10% hydride, polyphenyl silsesquioxane 100% phenyl, polyphenyl-methyl silsesquioxane 90% phenyl, 10% methyl, phenylsilsesquioxane-dimethylsiloxane copolymer 70% phenyl, 30% dimethyl, polyphenyl-propylsilsesquioxane 70% phenyl, 30% propyl, polyphenyl-vinylsilsesquioxane 90 % Phenyl, 10% vinyl, polycyclohexylsilsesquioxane silanol reactivity> 90% T7 cube, polycyclohexylsilsesquioxane silanol reactivity> 95% T7 cube, polycyclopentylsilsesquioxane (H-substituted) hydrosilylation T8 cube, polycyclopentylsilsesquioxane (methacryloxy substituted) polymerizable T8 cube, polycyclopentylsilsesquioxane (all H substituted) T8 cube, poly (2-chloroethyl) silsesquioxane, T8 stand Body, poly (2-chloroethyl) such as silsesquioxane, polysilsesquioxane; and the like.

  Examples of the titanium-based alkoxides include tetraalkoxytitanium having 1 to 10 carbon atoms in the alkoxy group such as tetraethoxytitanium; titanium di-n-butoxide (such as bis-2,4-pentanedionate).

  Aluminum-based alkoxides include aluminum triisopropoxa; aluminum disec-butoxide ethyl acetoacetate, etc., aluminum dialkoxy diketonates; aluminum-sec-butoxide bis (ethyl acetoacetate), etc., aluminum alkoxy bisdiketonates An aluminum tridiketonate such as aluminum tri-2,4-pentanedionate; and an aluminum carboxylate such as aluminum acetate and aluminum acrylate.

  Zirconium-based alkoxides include zirconium hydroxide; tetra-n-propoxyzirconium, etc., tetraalkoxyzirconium whose alkoxy group has 1 to 10 carbon atoms; zirconium methacryloxyethyl acetoacetate tri-n-propoxide, etc., zirconium trialkoxy Diketonates; zirconium di-iso-propoxides (bis-2,2,6,6-tetramethyl-3,5-heptadionate), zirconium dialkoxy diketonates; zirconium tetra-2,4-pentanedio Zirconium tetraketonates such as nates; zirconium carboxylates such as zirconyl dimethacrylate and zirconyl propionate can be exemplified.

  Examples of the hafnium-based alkoxides include tetraalkoxy hafnium having 1 to 10 carbon atoms in an alkoxy group such as tetra-n-butylhafnium; hafnium tetraketonate such as hafnium tetra-2,4-pentanedionate; hafnium di-n- Examples include hafnium dialkoxy diketonates such as butoxide (bis-2,4-pentanedionate).

  Examples of yttrium-based alkoxides include trialkoxy yttrium having 1 to 10 carbon atoms in the alkoxy group such as yttrium triisopropoxide; yttrium tridiketonate such as yttrium tri 2,4-pentanedionate; yttrium acetate and yttrium acrylate And aluminum carboxylate.

  Examples of the organic filler include divalent or higher alcohols, phenols, carboxylic acids, amines, epoxies, and latexes.

  Examples of the dihydric or higher alcohol or phenol include ethylene glycol; diethylene glycol; triethylene glycol; polyethylene glycol and polypropylene glycol having a molecular weight of 200 to 35,000; 1,3-propanediol; 1,4-butanediol; 1,6-hexanediol; 1,8-octanediol; 1,9-nonanediol; 1,10-decanediol; 1,11-undecanediol; 1,4-dibenzyl alcohol; 1,4-dihydroxybenzene; 1,3-dihydroxybenzene; 4,4′-dihydroxybiphenyl; 2,2′-dihydroxybiphenyl; 4-hydroxyphenethyl alcohol; 3- (4- Droxyphenyl) -1-propanol; hydroquinone bis (2-hydroxyethyl) ether; 4,4′-isopropylidenebis [2- (2,6-dibromophenoxy) ethanol]; 2- (2-hydroxyethoxy) phenol Trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol; 2-hydroxyphenethyl alcohol; 3-hydroxyphenethyl alcohol; 1-phenyl-1,2-ethanediol; 2-benzyloxy; -1,3-propanediol; 3-phenoxy-1,2-propanediol; 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene; 2,2-biphenyldimethanol; 3,5-dihydroxy Benzyl alcohol; hydrobenzoin; α-naphthol Benzopinacol; 2-hydroxybenzyl alcohol; 1,2-benzenedimethanol; 2,2- (1,2-phenylenedioxy) diethanol; 3-hydroxybenzyl alcohol; 1,3-benzenedimethanol; α, α, α ′, α′-tetramethyl-1,3-benzenedimethanol; α, α, α ′, α′-tetrakis (trifluoromethyl) -1,3-benzenedimethanol; 1,4-benzenedimethanol Methanol, 3-aminobenzyl alcohol; α, α, α ′, α′-tetramethyl-1,4-benzenedimethanol; α, α, α ′, α′-tetrakis (trifluoromethyl) -1,4- Benzenedimethanol hydrate; phenylhydroquinone; 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluoro-4,4′-bipheno Bis (4-hydroxyphenyl) methane; bisphenol A; bisphenol P; bisphenol M; 4,4 ′-(hexafluoroisopropylidene) diphenol; 2,2-bis (4-hydroxy-3-methylphenyl) ) Propane; 1,1,1-tris (4-hydroxyphenyl) ethane; hexestrol; tetrafluorohydroquinone; 1,1′-bi-2-naphthol; 4,4 ′-(9-fluorenylidene) diphenol; 2,7-dihydroxyfluorene; 4,4 ′-(1,3-adamantane) diphenol; N, N′-bis (2-hydroxyethyl) oxamide; 1,5-dihydroxynaphthalene; 1,6-dihydroxy Naphthalene; 1,7-dihydroxynaphthalene; 2,3-dihydroxynaphthalene; 2,6-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; UC-CARB100, UH-CARB50, UH-CARB100, UH-CARB200, UH-CARB300, UM-CARB90 (1/1), UM manufactured by Ube Industries, Ltd. Polycarbonate diol having a molecular weight of 250 to 10,000 such as CARB90 (3/1); Polyether diol having a molecular weight of 250 to 10,000 such as polytetrahydrofuran; Polyester diol having a molecular weight of 250 to 10,000; Molecular weight 250 to 10 , 1,000 polycaprolactone diols; hydroquinone; 4,8-bis (hydroxymethyl) -tricyclo [5.2.1.0 (2,6)] decane; 1,4-cyclohexanemethanol; 4,4'-isopropylidene Dendicyclohexano 1,5-decalindiol; 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol; 2,2,3,3,4,4,5,5 , 6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol; Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425 manufactured by Chisso Corporation Dihydric alcohols or phenols such as polydimethyl hydroxide (phenyl) siloxane at both ends; trimethylol ethane; trimethylol propane; 2- (hydroxymethyl) -1,3-propanediol, 2-ethyl-2 -(Hydroxymethyl) -1,3-propanediol; 1,1,1, -tris (hydroxymethyl) ethane; 1,2,4-butanetriol; glycerol; 1,3,5-trimethylolbenzene; 1,2,4-trihydroxybenzene; 1,3,5-trihydroxybenzene; pyrogallol; 1,3,5-tris (2-hydroxyethyl) cyanuric acid; Pentaerythritol; di (trimethylolpropane); DL-xylose; D-xylose; L-xylose; 1,1,1,5,5,5-hexafluoro-2,2 1,4,4-pentanetetrol; 1,2,4,5-tetramethylolbenzene; calix [4] arene; tetravalent alcohol or phenol such as; and pentavalent alcohol such as L-mannose and xylitol; Dipentaerythritol, tripentaerythritol, inositol, α-cyclodextrin, β-cyclodextrin, γ- Cyclodextrin, calix [6] arene, calix [8] hexahydric or higher alcohol or a phenol such as arene and the like.

  Examples of the divalent or higher carboxylic acid include terephthalic acid; succinic acid; glutaric acid; adipic acid; 1,10-decanedicarboxylic acid; perfluoroadipic acid; perfluorosuberic acid; 1,3-adamantane dicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; trans-1,4-cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid; 1,2-cyclohexanecarboxylic acid; Divalent carboxylic acids such as carboxylated polydimethyl (phenyl) siloxane at both ends, such as Silaplane FM-6611, Silaplane FM-6621, Silaplane FM-6625, etc .; Trimesic acid; 1,2,3-benzene Carboxylic acid; 1,3,5-cyclohexane 1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid; trivalent carboxylic acid; 1,2,4,5-benzenetetracarboxylic acid; cyclobutanetetracarboxylic acid; , 2,3,4,5,6-hexacarboxylic acid and other tetravalent or higher carboxylic acids.

  Examples of divalent or higher amines include ethylenediamine; 1,3-diaminopropane; 1,2-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; hexamethylenediamine; 1,7-diamino. 1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane; 4,4′-diaminobenzanilide; bis (hexamethylene) Triamine; 4- (aminomethyl) -1,8-octanediamine; Tris (2-aminoethylamine); 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine; 5-amino-1,3 , 3-Trimethylcyclohexanemethylamine; 4,4′-methylenebis (2-methylcyclohexyl) 1,3-cyclohexanebis (methylamine); 4,4'-methylenebis (cyclohexylamine); 4,4'-ethylenedianiline; 3,3'-methylenedianiline; 4,4'-methylene 4,4'-methylenebis (3-chloro-2,6-dimethylaniline); 4,4'-oxydianiline; 4,4'-ethylenedi-m-toluidine; o-tolidine; tetramethylbenzidine; 1,4-phenylenediamine; 1,2-phenylenediamine; 1,3-phenylenediamine; functional resin monomers manufactured by Mitsui Chemicals, such as APB, APB-N, bisaniline-P, bisaniline-M, and NBDA; 2 , 3-Diaminotoluene; 4-chloro-1,2-phenylenediamine; 4,5-dichloro-1,2-phenylenediamine; 4-methoxy-1,2-phenylenediamine; 2,6-diaminotoluene; 4,4′-diaminooctafluorobiphenyl; 3,3-diaminobenzidine; 2,4-diaminotoluene; 3,5-diaminobenzyl alcohol; 1,2,4,5, -benzenetetramine; 4,4 ′-(hexafluoroisopropylidene) dianiline; 3,3′-dimethoxy Benzidine; pararosaniline base; 3,3′-dimethylnaphthidine; 1,5-diaminonaphthalene; 2,7-diaminofluorene; 1,8-diaminonaphthalene; 9,10-diaminophenanthrene; Diaminonaphthalene; 3,7-diamino-2-methoxyfluorene; melamine; 2,4,6-tria Minopyrimidine; 2, -dimethyl-1,3-propanediamine; spermidine; spermine; diethylenetriamine; trans-1,4-diaminocyclohexane; Silaplane FM-3311, Silaplane FM-3321, Silaplane FM manufactured by Chisso Corporation -3325, etc., both ends aminated polydimethyl (phenyl) siloxane;

  Examples of the divalent or higher epoxy include bisphenol A type epoxy resin; brominated bisphenol A epoxy resin; orthocresol novolac type epoxy resin; alicyclic epoxy resin; DCPD epoxy resin; brominated novolak type, phenol novolac type, biphenyl. Examples include polyphenol type epoxy resins; 1,3,5-tris (2,3-epoxypropyl) isocyanurate, etc., polyglycidylamine type epoxy resins; alcohol type epoxy resins; ester type epoxy resins; it can. The above epoxy compounds are described in P1126 to P1135 of “14705 Chemical Products” issued by Chemical Industry Daily. Examples of other divalent or higher epoxies include both ends epoxidized polydimethyl (phenyl) siloxane such as Silaplane FM-5511, Silaplane FM-5521, Silaplane FM-5525, etc. manufactured by Chisso Corporation.

  Examples of the latex include products such as Nippon Synthetic Rubber Co., Ltd., Nippon A & L Co., Ltd., and Nippon Zeon Co., Ltd., for example, trade names such as pilatex and Nipol series.

  Particularly suitable raw material fillers include pentaerythritol, trimesic acid, dipentaerythritol, polytetrahydrofuran, myo-inositol, polyethylene glycol, tetraethoxysilane, methyltriethoxysilane, 1,4-phenylenediamine, hexamethylenediamine, Consisting of at least one selected from the group consisting of 4,4′-biphenol, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, N, N′-bis (hydroxyethyl) oxamide, and bisphenol Can be illustrated. The effect of the functional filler containing these raw material fillers as constituent components is proved in Examples described later.

  The functional filler according to the present invention is preferably modified with 0.01 parts by mass or more of polylactic acid (A) per 100 parts by mass of the raw material filler. If polylactic acid (A) is 0.01 mass part or more, the dispersibility in the polylactic acid which is a matrix polymer can be sufficiently secured, and the heat resistance, moldability, and mechanical strength of the resulting resin composition are also improved. It is enough. More preferably, it is 0.1 weight part or more of polylactic acid (A) per 1 weight part of raw material fillers, and still more preferably 0.2 to 2000 weight parts.

  The method of modifying the raw material filler with the polylactic acid (A) is not particularly limited, and examples thereof include a method of dehydrating polymerization of lactic acid and / or ring-opening polymerization of lactide in the presence of the raw material filler. In addition, these dehydration polymerization and ring-opening polymerization can utilize the method of Unexamined-Japanese-Patent No. 9-143253 and the method of Unexamined-Japanese-Patent No. 7-208551.

More specifically,
Mixing a raw material filler with a solution of lactic acid and / or lactide or a melt of lactic acid and / or lactide; and
By polymerizing lactic acid and / or lactide, the functional filler of the present invention can be produced by a method including a step of modifying the surface or terminal of the raw material filler with polylactic acid. The method for producing such a functional filler is also one aspect of the present invention. Hereinafter, conditions and the like will be described for each process.

  First, a solution of lactic acid and / or lactide or a melt of lactic acid and / or lactide and a raw material filler are mixed. As the solvent of the solution, toluene can be preferably used. In the subsequent polymerization step, the reaction is carried out while removing water generated by the polymerization. In such a reaction, benzene and toluene are generally used. However, toluene is preferably used because the boiling point of benzene is relatively low and the reaction may not proceed well. Moreover, since the melting point of lactic acid is about 53 ° C. and the melting point of lactide is 124 ° C., the melt can be easily formed by setting the temperature to be higher than these. The mixing method is not particularly limited, and the raw material filler may be added to and mixed with the above solution or melt, or after mixing lactic acid and the raw material filler, a solvent may be added or lactic acid or the like may be melted. .

  The ratio of lactic acid and the like to the raw material filler is the amount of polylactic acid (A) to be bonded to the raw material filler, that is, the number of polylactic acid (A) to be bonded and individual molecular weights, and polylactic acid not bonded to the raw material filler. What is necessary is just to adjust suitably according to whether it wants to remain | survive. Moreover, it adjusts also with the kind of raw material filler. For example, in the case of a dihydric alcohol having only two functional groups to which polylactic acid can bind, the amount of lactic acid and the like should be relatively small. On the other hand, when using a raw material filler capable of binding a large amount of polylactic acid or the like to the surface, such as surface-modified silica, the amount of lactic acid or the like may be relatively large. Further, the concentration of the solution of lactic acid or the like is not particularly limited, but can be, for example, about 40 to 80% by mass. In addition, at the stage of the process, it is not necessary to be a complete solution, and a part of lactic acid or the like may be in a suspended state without being dissolved.

  Next, the temperature of the mixed solution obtained in the mixing step is raised to advance the polymerization reaction. Simultaneously with the polymerization of lactic acid, polylactic acid binds to the reactive group on the surface or terminal of the raw material filler. At this time, a general polymerization catalyst may be added, but it is preferable not to use a catalyst in consideration of the possibility of not refining the functional filler. The polymerization reaction proceeds by raising the temperature to about 100 to 250 ° C. Further, the polymerization reaction can be further advanced by introducing an inert gas such as argon gas or nitrogen gas or removing water in the reaction system. The reaction time is not particularly limited, but can be about 5 to 20 hours. The polymerization degree of polylactic acid can be adjusted by adjusting the reaction temperature and reaction time according to the reaction substrate.

  In addition to the above production method, the polylactic acid to be bound can be synthesized separately and the polylactic acid can be bound to the raw material filler. This method is effective when bonding special polylactic acid such as a block copolymer. Before the polylactic acid is bonded to the raw material filler, the terminal hydroxyl group or terminal carboxyl group of the polylactic acid may be activated.

  After completion of the reaction, the reaction mixture is dissolved in chloroform, dioxane, etc., then methanol or ethanol, which is a poor solvent for polylactic acid, is gradually added to reprecipitate the functional filler preferentially, and this precipitate is recovered. It may be purified. However, it may be used as it is as a mixture with unbound polylactic acid.

  In the said manufacturing method, the functional filler composition containing the polylactic acid which is not couple | bonded with raw material slurry is manufactured by using excessive amount of lactic acid and / or lactide with respect to raw material filler, and not performing unnecessary refinement | purification. You can also Such a functional filler composition and its production method are also one aspect of the present invention.

The resin composition of the present invention is
Containing the functional filler of the present invention and polylactic acid which is a matrix polymer;
It is characterized in that at least a part of the polylactic acid interacts with the polylactic acid modifying the surface or terminal of the functional filler. In this resin composition, the polylactic acid that is a matrix polymer and the polylactic acid bonded to the functional filler can interact with each other. Therefore, the functional filler crosslinks a plurality of matrix polymers, and the heat resistance and strength of the composition material. Etc. are remarkably enhanced. Hereinafter, polylactic acid which is a matrix polymer may be referred to as “polylactic acid (B)”.

  As the polylactic acid (B), which is a matrix polymer, one that at least a part thereof can interact with the polylactic acid (A) bonded to the functional filler is used. If at least a part of the polylactic acid (B) can interact with the polylactic acid (A), a plurality of polylactic acids (B) can be cross-linked to the polylactic acid (A) and the heat resistance and the like can be improved. It is preferable to use polylactic acid (B) exhibiting a strong interaction with polylactic acid (A) in order to improve the above. For example, when polylactic acid (A) is poly L-lactic acid, it is preferable to use poly D-lactic acid as polylactic acid (B). Moreover, a mixture of polylactic acid may be used as polylactic acid (B), and in this case, a functional filler whose surface or terminal is modified with a mixture of polylactic acid may be used.

  Poly L-lactic acid and poly D-lactic acid are obtained, for example, by directly condensing L-lactic acid or D-lactic acid obtained from a plant raw material by fermentation, as disclosed in JP-A-9-143253. be able to. Moreover, as disclosed in JP-A-7-206851, a cyclic dimer of lactic acid (D-lactide, L-lactide) obtained by thermally decomposing a low molecular condensate of lactic acid (lactic acid oligomer) is obtained. The same poly L-lactic acid and poly D-lactic acid can be obtained by ring-opening polymerization.

  The preferred molecular weight of the polylactic acid (B) used in the present invention has its own optimum value determined by the purpose, application, required performance, or molding method. Usually, the number average molecular weight (Mn) in terms of polystyrene is 50,000 or more, preferably 100,000 or more, more preferably 120,000 to 500,000. The number average molecular weight in the present invention is measured by GPC (gel permeation chromatography) in a 1,1,1,3,3,3-hexafluoro-2-isopropanol solvent. In addition, the weight average molecular weight of polylactic acid is 1.1-5xMn normally, Preferably it is 1.1-3xMn. However, in special applications such as foaming applications and blown film applications, it is possible to use them sufficiently outside this range.

  You may mix | blend the unbonded polylactic acid produced | generated at the time of manufacture of a functional filler with the resin composition of this invention. This polylactic acid may be added in addition to the functional filler and matrix polymer of the present invention, but is included in the functional filler composition of the present invention described above. Therefore, when the functional filler composition of the present invention and the matrix polymer are mixed, the polylactic acid is naturally blended. The unbound polylactic acid produced during the production of the functional filler may be hereinafter referred to as “polylactic acid (C)”.

  When at least part of polylactic acid (C) interacts with polylactic acid (B), for example, polylactic acid (A) or polylactic acid (C) is poly-L-lactic acid, and polylactic acid (B) is poly-D. -When it is lactic acid, or when polylactic acid (A) or polylactic acid (C) is poly-D-lactic acid and polylactic acid (B) is poly-L-lactic acid, polylactic acid (A) and / or polylactic acid At least a part of (C) and the polylactic acid (B) can form a stereocomplex.

  The presence or absence of a stereocomplex of the polylactic acid (B) which is the functional filler of the present invention and the matrix polymer, or the polylactic acid (B) and the polylactic acid (C) is measured by, for example, DSC in the temperature rising process. In this case, heat generation of crystallization is observed at a lower temperature (Tc2) than the crystallization temperature (Tc1) of normal poly L-lactic acid or poly D-lactic acid, and the melting point (Tm1) of poly L-lactic acid or poly D-lactic acid. ) It can be easily judged from a new melting point (Tm2) at a higher temperature. The heat of fusion (ΔHm2) at the melting point (Tm2) is proportional to the amount of poly D-lactic acid in poly L-lactic acid or the amount of poly L-lactic acid in poly D-lactic acid. This makes it possible to quantify the amount of stereocomplex in poly L-lactic acid or the amount of stereocomplex in poly D-lactic acid.

  The functional filler and / or functional filler composition in the resin composition according to the present invention is preferably 0.01 parts by mass or more per 100 parts by mass of the matrix polymer. If it is 0.01 mass part or more, the physical property improvement effect by addition of a functional filler is fully securable. More preferably, it is 0.5 mass part or more, More preferably, it is 1 mass part or more. On the other hand, when the functional filler is excessively added, the strength of the resin composition may be lowered. Therefore, the addition amount of the functional filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less per 100 parts by mass of the matrix polymer.

  The heat resistance of the resin composition according to the present invention is preferably heat resistance with a deformation amount of less than 10 mm in a heat sag test at 110 ° C. or higher. Here, the heat sag test is performed for 1 hour at a temperature of 110 ° C. or higher according to JIS K7195. The test piece is formed by cutting a hot press into a predetermined size with a hot cutter. Here, good heat resistance means a case where the amount of deformation is less than 10 mm. More preferable heat resistance means that the amount of deformation is small in a higher temperature heat sag test. If the deformation at 110 ° C. or higher is 10 mm or more, the heat resistance is insufficient and it is inappropriate depending on the application. More preferable heat resistance is a deformation amount of less than 10 mm in a heat sag test of 120 ° C. or more, and further preferably 130 ° C. or more and less than 10 mm.

  The resin composition according to the present invention preferably has high transparency, and the light transmittance at 550 nm when the resin composition according to the present invention is molded into a sheet sample having a thickness of 0.2 mm is 70% or more. Is more preferable, and 75% or more is more preferable.

  Further, in the resin composition according to the present invention, the uniformly dispersed functional filler functions as a crystal nucleating agent, so that the crystallization speed of the resin composition is increased, and the molding speed, stretching temperature, and stretching ratio can be improved. Thus, the physical properties and moldability of the obtained molded product can be improved, and the application can be expanded. Further, even when crystallized, since the spherulite size is small, transparency is maintained, and the brittleness of the molded body is improved without breaking at the spherulite interface.

  The resin composition according to the present invention preferably has a crystallinity of 25% or more. If the degree of crystallinity is less than 25%, the heat resistance and elastic modulus are low, so the heat resistance and mechanical properties of the molded article are insufficient depending on the application. More preferably, it is 30% or more, More preferably, it is 35-80%. The crystallinity of the resin composition can be measured using a differential scanning calorimeter such as Rigaku DSC8230 manufactured by Rigaku Corporation.

  The resin composition according to the present invention can be made into a heat-resistant flame retardant material by kneading various flame retardants. Examples of the flame retardant include halogen antimony flame retardants and environment-friendly flame retardants, but the environment-friendly flame retardants are mainly used.

  Examples of environment-friendly flame retardants include silicone flame retardants, phosphorus flame retardants, metal hydroxide flame retardants, and nitrogen flame retardants.

  Examples of the silicone flame retardant include SZ6018, which is phenyl silicone manufactured by Dow Corning Silicone, DC4-7081, which is methacryl group-containing polymethylsiloxane, manufactured by Dow Corning Silicone, polycarbonate + MB50-315 which is polydimethylsiloxane, X40-9805 which is methylphenyl silicone manufactured by Shin-Etsu Silicone, XC99-B5664 which is phenyl silicone manufactured by GE Toshiba Silicone, and the like.

  Examples of phosphorus flame retardants include AP flame retardants, OP flame retardants, TPP flame retardants sold by Clariant, etc .; aromatic condensed phosphate esters such as PX-200 made by Daihachi Chemical Co., Ltd. ; Ammonium polyphosphates such as Fikat FCP730 manufactured by Suzuhiro Chemical Co .; and triphenyl phosphate sold by Daihachi Chemical Co., Ltd.

  Examples of the metal hydroxide flame retardant include BF013ST (average particle size 1 μm, Kismer 5A), which is aluminum hydroxide manufactured by Nippon Light Metal Co., Ltd.

  Examples of the nitrogen-based flame retardant include Stabaxol I which is a mixture of bis (diisopropylphenyl) carbodiimide main components manufactured by Rhein Chemie; Stavaxol P which is a mixture of 95% aromatic monocarbodiimide and 5% silica manufactured by Rhein Chemie; Nissan Melamine compounds such as melamine cyanurate, dimelamine phosphate, melamine borate, such as MC-440 manufactured by Chemical Industry Co., Ltd .; “Apinon” series manufactured by Sanwa Chemical Co., Ltd., “Melar” series manufactured by Monsanto, etc. Examples thereof include guanidine compounds such as acid guanidine and guanine phosphate phosphate.

  The resin composition according to the present invention can further improve various characteristics such as mechanical characteristics and gas barrier characteristics by kneading the raw material filler of the functional filler of the present invention.

  Further, by adding the functional filler of the present invention, it is possible to improve the dispersibility or compatibility between the matrix polymer and other polymers (polycarbonate, polyethylene terephthalate, polypropylene, etc.) and additives (dyes, etc.).

Although it does not specifically limit as a manufacturing method of the resin composition which concerns on this invention, For example,
Mixing a raw material filler with a solution of lactic acid and / or lactide or a melt of lactic acid and / or lactide;
A step of polymerizing lactic acid and / or lactide to modify the surface or terminal of the raw material filler with polylactic acid to form a functional filler; and the functional filler is polylactic acid which is a matrix polymer, and at least one of them And a step of mixing with a part that interacts with polylactic acid that modifies the surface or terminal of the functional filler. Such a method for producing a resin composition is also one aspect of the present invention.

  In the above production method, the functional filler and the matrix polymer may be mixed in a solvent. However, since a drying step is required and the solvent itself may be harmful to the living body, it is preferable to melt and mix at a temperature equal to or higher than the melting point of at least one component.

  In the method for producing a resin composition according to the present invention, as a method for removing the solvent used in the production of the functional filler, a normal solvent removing method can be adopted, but during mixing with a lab plast mill or a twin screw extruder, A method of removing while heating under atmospheric pressure or reduced pressure is preferably used.

  A molded body comprising the resin composition according to the present invention is also one aspect of the present invention. Examples of such a molded body include a molded body by injection molding, a molded body by extrusion molding, a molded body by inflation method, a molded body by blow molding method, a molded body by transfer molding method, a molded body by compression molding method, and a fiber. Structures and other molded articles obtained by a molding method usually used for plastic molding can be mentioned. When applied to each molding method, the melting characteristics, solidification, and crystallization characteristics of the resin composition are important factors. However, in the present invention, any molding method can be easily optimized.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Production Example 1 Manufacture of functional filler composition with surface treated with low molecular weight polylactic acid [1] Manufacture of surface aminated silica and manufacture of D-form modified functional filler composition using the silica (1) Surface aminated silica After the dispersion of 56 g of Cyruspher C-1504 (average particle size: 4 μm), spherical silica made by Fuji Silysia, in 1.5 l of ethanol to which 75 ml of water was added, 3-aminopropyltriethoxysilane 15 g was added and stirred at room temperature for 24 hours.

  The silica particles were filtered under reduced pressure, washed with ethanol, and then dried at 100 ° C. to obtain 62 g of surface aminated silica. The obtained surface aminated silica was almost transparent. This indicates that the surface of the spherical silica is aminated and the aggregation between the silicas is eliminated.

(2) Production of D-form-modified functional filler composition <Sample 1>
5 g of the surface aminated silica obtained in (1) was dispersed in 50 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 140 ° C. overnight while performing argon bubbling to perform dehydration polymerization. It was.

  After the completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container, and cooled and solidified to obtain about 30 g of a yellowish brown almost transparent D-form-modified functional filler composition.

  The fact that the obtained D-form-modified functional filler composition is almost transparent indicates that the aggregation of the silica particles has been eliminated by bonding poly D-lactic acid to the surface of the silica particles.

(3) Production of D-form-modified functional filler composition <Sample 2>
10 g of the surface aminated silica obtained in (1) was dispersed in 50 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 140 ° C. overnight while performing argon bubbling to perform dehydration polymerization. It was.

  After the completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container, and cooled and solidified to obtain about 34 g of a yellowish brown almost transparent D-form-modified functional filler composition. The fact that the obtained D-form-modified functional filler composition is almost transparent indicates that the aggregation of the silica particles has been eliminated by bonding poly D-lactic acid to the surface of the silica particles.

(4) Production of D-form-modified functional filler composition <Sample 3>
Dissolve and disperse 40 g of the surface aminated silica obtained in (1) and 80 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) in 120 ml of toluene, and remove water while refluxing using a test tube in an argon atmosphere. By performing dehydration polymerization, a yellowish brown almost transparent D-form-modified functional filler composition liquid was obtained. The fact that the obtained D-form-modified functional filler composition is almost transparent indicates that the aggregation of the silica particles has been eliminated by bonding poly D-lactic acid to the surface of the silica particles.

  The toluene solution of this D-form-modified functional filler composition was used as it was in the next experiment.

[2] Production of D-form-modified functional filler composition <Sample 4>
16.5 g of a methanol suspension of silica sol manufactured by Nissan Chemical Co., Ltd. was dispersed in 50 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred overnight at 140 ° C. while bubbling with argon. Polymerization was performed.

  After completion of the reaction, the mixture was cooled and solidified, and the solid was scraped with a spatula to obtain about 27 g of a colorless and transparent D-form-modified functional filler composition.

[3] Manufacture of surface epoxidized silica and manufacture of D-form modified functional filler composition using the silica (1) Manufacture of surface epoxidized silica Pyrospher C-1504, a spherical silica made by Fuji Silysia 52 g (average particle diameter: 4 μm) was dispersed in 1.5 l of ethanol to which 75 ml of water was added, and then acetic acid was added to adjust the pH to about 4. Next, 16 g of 3-glycidoxypropyltrimethoxysilane was added and stirred at room temperature for 24 hours.

  The silica particles were filtered under reduced pressure, washed with ethanol, and then dried at 100 ° C. to obtain 54 g of surface epoxidized silica.

(2) Production of D-form-modified functional filler composition <Sample 5>
10 g of the surface epoxidized silica obtained in (1) is dispersed in 50 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 140 ° C. overnight while performing argon bubbling to perform dehydration polymerization. It was.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 30 g of a colorless and almost transparent D-form-modified functional filler composition. The fact that the obtained D-form-modified functional filler composition is almost transparent indicates that silica particles are dispersed in poly-D-lactic acid in a state of almost primary particles.

[4] Production of D-form-modified functional filler composition <Sample 6>
10 g of Kunipia P, which is montmorillonite manufactured by Kunimine Co., was dispersed in 100 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 140 ° C. overnight while performing argon bubbling to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 65 g of a grayish green D-form-modified functional filler composition.

[5] Production of D-form-modified functional filler composition <Sample 7>
50 g of aerosil silica, which is silica particles manufactured by Nippon Aerosil Co., Ltd., and 50 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) were mixed. At the beginning of the reaction, Aerosil absorbed D-lactic acid to become a solid and was non-uniform, but when reacted at 140 ° C. with argon bubbling as it was, it gradually became a uniform solution. Further, dehydration polymerization was performed while stirring overnight.

  After the completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 32 g of a colorless and almost transparent D-form-modified functional filler composition. The fact that the obtained D-form-modified functional filler composition is almost transparent indicates that the aggregation of the silica particles has been eliminated by bonding poly D-lactic acid to the surface of the silica particles.

[6] Production of L-form-modified functional filler composition <Sample 8>
50 g of Aerosil Silica, which is silica particles manufactured by Nippon Aerosil Co., Ltd., and 50 g of L-lactic acid (manufactured by Nacalai Tesque, 90 mass% aqueous solution) were mixed. At the beginning of the reaction, Aerosil absorbed L-lactic acid and became a solid, which was non-uniform. However, when the reaction was carried out at 140 ° C. with argon bubbling as it was, it gradually became a homogeneous solution. Further, dehydration polymerization was performed while stirring overnight.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container as it was, and cooled and solidified to obtain about 32 g of a colorless and almost transparent L-form-modified functional filler composition. The fact that the obtained L-form-modified functional filler composition is almost transparent indicates that the silica particles are dispersed in poly-L-lactic acid in a state of almost primary particles.

[7] Production of D-form-modified functional filler composition <Sample 9>
3.7 g of fibrous hydroxyapatite manufactured by Ube Materials Co. was dispersed in 37 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by weight aqueous solution) and stirred overnight at 140 ° C. while argon bubbling to perform dehydration polymerization. Went.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container as it was and solidified by cooling to obtain about 27 g of a white D-form-modified functional filler composition.

[8] Production of D-form-modified functional filler composition <Sample 10>
The pulp sheet 9g was loosened into fibers with a mixer, and water was partially removed to obtain about 40 g of lump. The whole mass, 50 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution), and 50 g of water were added and stirred overnight at 140 ° C. while performing argon bubbling to perform dehydration polymerization.

  After completion of the reaction, the mixture was cooled and solidified, and then scraped with a spatula to obtain about 33 g of a yellowish brown D-form-modified functional filler composition.

[9] Production of D-form-modified functional filler composition <Sample 11>
2.5 g of pentaerythritol was dispersed in 73 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 140 ° C. for 2 days while performing argon bubbling to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 69 g of a colorless and transparent D-form-modified functional filler composition.

[10] Production of D-form-modified functional filler composition <Sample 12>
Pentaerythritol (5 g) was dissolved in 73 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 140 ° C. for 2 days while performing argon bubbling to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 66 g of a colorless and transparent D-form-modified functional filler composition.

[11] Production of D-form-modified functional filler composition <Sample 13>
2.5 g of trimesic acid was dispersed in 71 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred overnight at 140 ° C. while performing argon bubbling to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container as it was and solidified by cooling to obtain about 70 g of a white D-form-modified functional filler composition.

[12] Production of D-form-modified functional filler composition <Sample 14>
5 g of dipentaerythritol was dissolved in 108 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred overnight at 140 ° C. while carrying out argon bubbling to carry out dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 73 g of a colorless and transparent D-form-modified functional filler composition.

[13] Production of D-form-modified functional filler composition <Sample 15>
30 g of Aerosil Silica 300, which is silica nanoparticles manufactured by Nippon Aerosil Co., Ltd., and 300 g of D-lactic acid (Pureac Co., 90 mass% aqueous solution) were mixed. At the beginning of the reaction, Aerosil absorbed D-lactic acid to become a solid and was non-uniform, but when reacted at 140 ° C. with argon bubbling as it was, it gradually became a uniform solution. Further, dehydration polymerization was performed while stirring overnight.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 220 g of a colorless and almost transparent D-form-modified functional filler composition.

[14] Production of D-form-modified functional filler composition <Sample 16>
100 g of Platex-LB (38.9 mass% aqueous solution), a latex manufactured by Nippon A & L Co., Ltd., is mixed with 300 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90 mass% aqueous solution) at 130 ° C. with argon bubbling. The mixture was stirred overnight and further at 160 ° C. overnight to conduct dehydration polymerization (at the time of polymerization, the generation of bubbles was intense and more than half of the polymer flowed out).

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 70 g of a brown translucent D-form-modified functional filler composition.

[15] Production of D-form-modified functional filler composition <Sample 17>
Polytetrahydrofuran (molecular weight 650) 23.1 g was dissolved in 215 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling. Then, dehydration polymerization was performed.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 145 g of a colorless and transparent D-form-modified functional filler composition.

[16] Production of D-form-modified functional filler composition <Sample 18>
17.8 g of polytetrahydrofuran (molecular weight 250) is dissolved in 427 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling. Then, dehydration polymerization was performed.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 325 g of a colorless and transparent D-form-modified functional filler composition.

[17] Production of D-form-modified functional filler composition <Sample 19>
10.0 g of myo-inositol was dissolved in 1000 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling to perform dehydration polymerization. went.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 750 g of a substantially colorless and transparent D-form-modified functional filler composition.

[18] Production of D-form-modified functional filler composition <Sample 20>
90 g of polyethylene glycol (molecular weight 600) is dissolved in 900 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by weight aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling to perform dehydration polymerization. Went.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container as it was, and then cooled and solidified to obtain about 790 g of a colorless and transparent D-form-modified functional filler composition.

[19] Production of D-form-modified functional filler composition <Sample 21>
Tetraethoxysilane (50.0 g) was dissolved in D-lactic acid (manufactured by Pulac Co., Ltd., 90 mass% aqueous solution) (450 g) and stirred at 130 ° C. overnight and at 160 ° C. overnight with argon bubbling to perform dehydration polymerization. went.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 250 g of a colorless and transparent D-form-modified functional filler composition.

[20] Production of D-form-modified functional filler composition <Sample 22>
37.5 g of methyltriethoxysilane was dissolved in 150 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling to perform dehydration polymerization. Went.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 95 g of a white D-form-modified functional filler composition.

[21] Production of D-form-modified functional filler composition <Sample 23>
61 g of Silaace S330, which is 3-aminopropyltrialkoxysilane manufactured by Chisso Corporation, is dissolved in 830 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and further bubbled with argon at 130 ° C. overnight. The mixture was stirred at 160 ° C. overnight to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container as it was, and cooled and solidified to obtain about 600 g of a yellow transparent D-form-modified functional filler composition.

[22] Production of D-form-modified functional filler composition <Sample 24>
35 g of Silaace S510, which is 3-glycidoxypropyltrialkoxysilane manufactured by Chisso Corporation, is dissolved in 900 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution), and at 130 ° C. overnight with argon bubbling Furthermore, it stirred at 160 degreeC overnight and performed dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 640 g of a colorless and transparent D-form-modified functional filler composition.

[23] Production of D-form-modified functional filler composition <Sample 25>
15 g of melamine was dissolved in 1071 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight while performing argon bubbling to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 750 g of a yellow opaque D-form-modified functional filler composition.

[24] Production of D-form-modified functional filler composition <Sample 26>
30 g of Silaplane FMDA11, which is a polydimethyl (phenyl) siloxane having both ends, produced by Chisso Corporation, is dispersed in 300 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and kept at 130 ° C. while bubbling with argon. The mixture was further stirred overnight at 160 ° C. for dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 220 g of a colorless and transparent D-form-modified functional filler composition.

[25] Production of D-form-modified functional filler composition <Sample 27>
30 g of Silaplane FM3311, a both-terminal aminated polydimethyl (phenyl) siloxane manufactured by Chisso Corporation, is dispersed in 300 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) at 130 ° C. while argon bubbling. The mixture was further stirred overnight at 160 ° C. for dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 230 g of a yellow transparent D-form-modified functional filler composition.

[26] Production of D-form-modified functional filler composition <Sample 28>
5.6 g of 1,4-phenylenediamine was dissolved in 515 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling. Dehydration polymerization was performed.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 350 g of a yellow transparent D-form-modified functional filler composition.

[27] Production of D-form-modified functional filler composition <Sample 29>
3.4 g of hexamethylenediamine was dissolved in 302 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling to perform dehydration polymerization. went.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 190 g of a yellow transparent D-form-modified functional filler composition.

[28] Production of L-form-modified functional filler composition <Sample 30>
8.3 g of 1,4-phenylenediamine was dissolved in 773 g of L-lactic acid (manufactured by Musashino Chemical Laboratory Co., Ltd., 90 mass% aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling. Then, dehydration polymerization was performed.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 590 g of a yellow transparent L-form-modified functional filler composition.

[29] Production of L-form-modified functional filler composition <Sample 31>
6.8 g of hexamethylenediamine was dissolved in 604 g of L-lactic acid (manufactured by Musashino Chemical Laboratory, Inc., 90% by weight aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling. Dehydration polymerization was performed.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 430 g of a yellow transparent L-form-modified functional filler composition.

[30] Production of D-form-modified functional filler composition <Sample 32>
9.3 g of 4,4′-biphenol was dissolved in 500 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling. Dehydration polymerization was performed.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 340 g of a colorless and transparent D-form-modified functional filler composition.

[31] Production of D-form-modified functional filler composition <Sample 33>
Zirconium tetrapropoxide (70%, 1-propanol solution) 50 g was dispersed in 250 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution) and bubbled with argon at 130 ° C. overnight and further at 160 ° C. The mixture was stirred overnight for dehydration polymerization.

  After completion of the reaction, the solid was transferred to a Teflon (registered trademark) container and allowed to cool to obtain about 170 g of a substantially white solid D-form-modified functional filler composition.

[32] Production of D-form-modified functional filler composition <Sample 34>
20 g of 1,3,5-tris (2-hydroxyethyl) cyanuric acid was dissolved in 1150 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution), and the mixture was further bubbled at 130 ° C. overnight with argon bubbling. The mixture was stirred overnight for dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 800 g of a colorless and transparent D-form-modified functional filler composition.

[33] Production of D-form-modified functional filler composition <Sample 35>
21.1 g of N, N′-bis (hydroxyethyl) oxamide was dissolved in 1200 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution), and it was overnight at 130 ° C. with argon bubbling and further at 160 ° C. The mixture was stirred overnight to conduct dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 845 g of a yellow transparent D-form-modified functional filler composition.

[34] Production of D-form-modified functional filler composition <Sample 36>
22.8 g of bisphenol was dissolved in 1200 g of D-lactic acid (manufactured by Pulac Co., 90 mass% aqueous solution) and stirred at 130 ° C. overnight and further at 160 ° C. overnight with argon bubbling to perform dehydration polymerization. .

  After the completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 837 g of a yellow transparent D-form-modified functional filler composition.

[35] Production of D-form-modified functional filler composition <Sample 37>
UC-CARB100 (molecular weight: 1000) 98 g of polycarbonate diol manufactured by Ube Industries, Ltd. was dissolved in 980 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution), and further at 130 ° C. overnight with argon bubbling. The mixture was stirred at 160 ° C. overnight to perform dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 755 g of a colorless and transparent D-form-modified functional filler composition.

[36] Production of D-form-modified functional filler composition <Sample 38>
150 g of polycarbonate diol UH-200 (molecular weight: 1000), which is a polycarbonate diol manufactured by Ube Industries, Ltd., is dissolved in 750 g of D-lactic acid (manufactured by Pulac Co., Ltd., 90% by mass aqueous solution), and at 130 ° C. while argon bubbling. The mixture was further stirred overnight at 160 ° C. for dehydration polymerization.

  After completion of the reaction, the fluid polymer was transferred to a Teflon (registered trademark) container and cooled and solidified to obtain about 645 g of a colorless and transparent D-form-modified functional filler composition.

  The D-form modified functional filler composition and the L-form modified functional filler composition obtained in Production Example 1 are shown together in Table 1.

  The viscosity of the functional filler composition solution whose surface is treated with poly-D-lactic acid or poly-L-lactic acid is higher than that of a melt of poly-L-lactic acid or poly-D-lactic acid polymerized under the same conditions without adding a filler. Indicated.

  When an organic filler such as pentaerythritol is used as a raw material filler (samples 11 to 14 and the like), the organic filler itself has a molecular level, so that the reaction proceeds effectively by sufficiently dispersing in D-lactic acid, and the functionality. The filler composition became transparent. On the other hand, in the state where the raw material organic filler such as trimesic acid has crystallinity and is not sufficiently dispersed in D-lactic acid in a solid state, a large granular material remained, and the functional filler composition appeared opaque. Moreover, most of the functional fillers using organic fillers as raw material fillers were colorless and transparent, and only the functional fillers whose surfaces were aminated were yellow.

Test Example 1 Confirmation of Bonding between Raw Material Filler and Polylactic Acid 1) IR was measured for sample 28 and 1,4-phenylenediamine as the raw material filler using an IR measuring device (MAGNA-IR760) manufactured by Nicoler. The results are shown in FIG.

  As shown in FIG. 1, a peak derived from an aromatic amine clearly appears in 1,4-phenylenediamine as a raw material filler. On the other hand, in sample 28, the peak derived from the amino group disappears, and the peak derived from the ester group appears clearly instead. Therefore, in Sample 28, it was proved that poly-D-lactic acid was bonded to both ends of 1,4-phenylenediamine.

  2) About the sample 24 and 3-glycidoxypropyl trialkoxysilane which is the raw material filler, NMR was measured using the NMR measuring apparatus (JMM GSX270) by JEOL. The results are shown in FIG.

  As shown in FIG. 2, in 3-glycidoxypropyltrialkoxysilane, peaks derived from a methoxy group and an epoxy group clearly appear. On the other hand, in sample 24, the peak derived from the methoxy group and the epoxy group has disappeared, and the peak derived from poly D-lactic acid appears instead. Therefore, in sample 24, it was proved that poly-D-lactic acid was bonded to both ends of 3-glycidoxypropyltrialkoxysilane.

Production Example 2 Production of Resin Composition Using Functional Filler Composition Homopoly L serving as a matrix for functional filler compositions 1 to 14 obtained by treating the surface with poly-D lactic acid or poly L-lactic acid obtained in Production Example 1 -Functionality by melting and kneading with lab kneader mill at 190 ° C for 15 minutes so that lactic acid (weight average molecular weight 200,000, Tm = 170 ° C) and weight ratio (the former: latter) are 1:10. A resin composition in which the filler was uniformly dispersed was obtained. The resin composition was pelletized and used for structural analysis and the like.

Test Example 2 Evaluation of Thermal Properties The obtained resin composition was heated and its behavior was observed. The results are shown in Table 2.

  None of the resin compositions containing the functional filler treated with poly-D-lactic acid excluding sample 8 showed a clear Tg and Tc, and had a melting point Tm1 derived from the matrix polymer homopoly-L-lactic acid around 170 ° C. In addition, a melting point Tm2 considered to be due to a stereocomplex formed from poly L-lactic acid and poly D-lactic acid was shown at around 216 ° C.

  In a resin composition containing a functional filler treated with poly-D-lactic acid, the low melting point Tm1 poly L-lactic acid part contributes to moldability, and the high melting point Tm2 stereocomplex part improves the heat resistance of the resin composition. It seems to contribute.

  From this, it can be seen that these resin compositions have characteristics of having good heat resistance as well as good moldability.

Test Example 3 Evaluation of moldability and physical properties of resin composition containing functional filler The resin composition obtained in Production Example 2 was hot-pressed at 190 ° C. for 3 minutes under a pressure of 30 MPa, and then rapidly cooled by a cold press. Thus, a 0.2 mm thick sheet was formed. The sheet was further heat treated at 130 ° C. for 1 hour to complete crystallization.

  These sheets were evaluated for transparency by light transmittance. The results are shown in Table 3.

  As shown in Table 3, when the functional filler of the present invention is not included, the quenched sheet is transparent, but the heat-treated sheet is whitened and becomes opaque. This indicates that large polylactic acid spherulites were formed by crystallization. Accordingly, in addition to the opacity, there is a certain heat resistance, but since there is no bonding force between large spherulite domains, it becomes very brittle in terms of physical properties and is not suitable for practical use. When the raw material filler is surface epoxidized silica, surface aminated silica, nano silica or aerosil silica (excluding sample 8 treated with poly L-lactic acid), both the quenched sheet and the heat treated sheet maintain transparency. This shows that the size of the formed spherulite is finer than the size of the wavelength of light even if it is crystallized.

  It can be seen that the dispersibility of the filler in the resin composition containing the functional filler composition using montmorillonite (Kunimine Co., Ltd., Kunipia P) as the raw material filler was greatly improved by the surface treatment with poly-D-lactic acid. Whitening by means that the size of the spherulites produced by the heat treatment has increased. Moreover, when fibrous hydroxyapatite is used as a raw material filler, it is considered that the composite became opaque because the particle size of fibrous hydroxyapatite is large.

  The crystallinity of the heat-treated sheet can be evaluated by DSC. In all cases, the melting point Tm1 of poly L-lactic acid is around 170 ° C., and the stereo of poly L-lactic acid and poly D-lactic acid is around 216 ° C. A melting point Tm2 by Compolex was observed. The amount of each component was calculated from the magnitude of heat of fusion at each melting point, but all showed almost the same heat of fusion, indicating that the sheet after heat treatment was sufficiently crystallized.

Test Example 4 Evaluation of heat resistance The heat resistance was evaluated by the heat sag test described above. The heat resistance of the sheet is evaluated by how much the leading edge of the sheet is lowered from the horizontal after the heat treatment test. If the falling distance is less than 10 mm, it indicates that the temperature is thermally stable. Table 4 shows the results of treatment at 130 ° C. for 1 hour.

  The quenched sheet containing no filler and the functional filler composition of Sample 8 were immediately deformed at 130 ° C. and showed a large amount of deformation. This is probably because the homopolylactic acid had a Tg of around 60 ° C., and the sheet easily deformed above that temperature. The filler-free sheet treated at 130 ° C. for 1 hour had heat resistance but was opaque.

  The resin composition (excluding the one containing the functional filler composition of Sample 8) forms a stereocomplex around countless fillers when melt-kneaded to form a sheet, and the filler gap It seems that the size of the stereocomplex crystal generated during this period has become small enough not to scatter visible light. Accordingly, a resin composition having transparency and excellent heat resistance can be obtained.

Production Example 3 Manufacture of pellets Pellets were manufactured using the functional filler of the present invention as materials for various molded products. Specifically, a functional filler and matrix poly-L-lactic acid are mixed with a functional filler: poly-L-lactic acid = 1: 9 using a twin-screw extruder (manufactured by Technovel, KZW15-30MG: L / D). Kneaded. At that time, the cylinder temperature was set to 180 ° C., the die temperature was set to 173 ° C., and the strands were directly cut with a pelletizer under air cooling conditions to obtain pellets having a length of 2 to 3 cm. The thermal properties of the obtained pellets are as follows.

  The kneading temperature is almost the same as the kneading temperature of ordinary polylactic acid, but when the polylactic acid is extruded from the nozzle, the solid stereocomplex functions as a crystal nucleating agent. As a result, the extruded polylactic acid composite material solidified at room temperature and can be cut directly without water cooling. Compared to homopoly L-lactic acid, it can be seen that the composite material has a polylactic acid stereocomplex melting point between 190 and 210 ° C. in addition to the homopolylactic acid melting point near 170 ° C. The portion of the stereocomplex increases as the amount of the functional filler added increases, and a crystallized polylactic acid composition is easily obtained.

  The composite pellet produced in Production Example 3 was applied to various molding methods as follows.

Production Example 4
Among the composite materials, those containing functional fillers using organic materials as raw material fillers were selected, and the content ratio of the functional fillers was changed and applied to injection molding. Specifically, the cylinder temperature was made higher than the stereo complex melting temperature, and the nozzle temperature was made lower than the stereo complex temperature. By making the cylinder temperature equal to or higher than the stereo complex melting temperature, the functional filler-containing polylactic acid composite material is sufficiently melted and uniformly mixed in the cylinder. Further, by setting the nozzle temperature to be equal to or lower than the stereo complex temperature, the injected stereo complex immediately becomes solid. The mold temperature was set to 27 ° C., and the molding cycle was set to 20 seconds. Further, according to JIS k-7110, the impact strength of each molded body was measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho. The results are shown in Table 6.

  The stereocomplex formed by the functional filler of the present invention and polylactic acid becomes a crystal nucleus after being injected to promote solidification, shorten the molding cycle, and improve the transparency of the molded body.

In addition, the impact strength of conventional homopolylactic acid is 2.6 KJ / m ² , but as described above, when the addition amount of the functional filler is 5 to 10% by mass, the impact strength is improved to about 3.0 KJ / m ^2. We were able to. However, when the addition amount of the functional filler was increased to 20% by mass, the impact strength was reduced.

Production Example 5
Among the pellets produced in Production Example 3, those containing functional fillers using pentaerythritol and aerosil silica as raw material fillers were applied to carbon dioxide foaming under the following conditions. The results are as follows.

  By forming a stereocomplex of the functional filler and polylactic acid, the stereocomplex was in a solid state even when the melting point of the normal polylactic acid was exceeded, and the effect of improving the viscosity of the polylactic acid was exhibited. Furthermore, due to the presence of the stereocomplex, the foamed polylactic acid molded product was crystallized at the foaming stage, and showed higher heat resistance than the amorphous polylactic acid foam. From the physical properties of the carbon dioxide foamed material, polylactic acid that is difficult to foam can be foamed by adding a small amount of filler, and its heat resistance is 100 ° C or higher, making it a PS foam used in daily life. It turns out that it can be replaced.

Production Example 6
Among the composites kneaded in Example 3, Sample 12, that is, a material containing a functional filler using pentaerythritol as a raw material filler, was melt-spun under the following conditions.

  The spinning of the composite is preferably performed at a melting point higher than that of homopolylactic acid and lower than that of a stereo complex. The reason is that when the stereo complex is dissolved, the viscosity becomes considerably low, and it may be difficult to form a molded product. Therefore, by spinning at a temperature not lower than the melting point of the homopolymer and not higher than the melting point of the stereo complex, the stereo complex is partially formed, whereby the homopolymers are connected to each other, and an apparently long molecule can be spun. In this example, a spinning temperature of 170 ° C. was set, and multifilaments were obtained by melt spinning. Further, since there is no change in viscosity, it is not necessary to improve the existing apparatus, and it is a feature of the present composite material that spinning can be performed.

Production Example 7
Of the pellets produced in Production Example 3, those containing functional fillers using dipentaerythritol and aerosil silica as raw material fillers were sheet-molded under the following conditions.

  As described above, when the amount of the functional filler added is large, the molded sheet has heat resistance from the time when it comes out of the T die. Such heat resistance is thought to be due to the fact that crystallization is facilitated by the stereocomplex and the mobility of polylactic acid molecules is restricted. The polylactic acid sheet released from the T-die also has both transparency and heat resistance, and can be subjected to secondary processing.

For example, the following can be realized by the present invention.
1. Improve the uniform dispersibility of fillers in liquids and polymers. Development of various additives, crystal nucleating agents, reinforcing materials and lubricants.
2. Filler pellets.
3. Improved physical properties and moldability of aliphatic polyesters including polylactic acid.
4). Improvement of heat resistance and mechanical strength of sheet, film, injection molded body, extruded molded body, blown film, fiber and other applied products.

It is a schematic diagram which shows the outline | summary of the functional filler of this invention. It is IR data of the functional filler of the present invention and its raw material filler. It is NMR data of the functional filler of the present invention and its raw material filler.

Explanation of symbols

1 ... Raw material filler 2 ... Polylactic acid bonded to filler surface

Claims (14)

  A functional filler comprising a raw material filler and polylactic acid, wherein a surface filler or a terminal of the raw material filler is modified with polylactic acid.   2. The functional filler according to claim 1, wherein the raw material filler has a functional group that can be chemically and / or physically bonded to a carboxyl group, a hydroxyl group, or a carbonyl group on the surface or terminal thereof.   The functional filler according to claim 1, wherein the raw material filler is an inorganic filler.   The functional filler according to claim 1, wherein the raw material filler is an organic filler.   The functional filler according to any one of claims 1 to 4, wherein the polylactic acid that modifies the surface or terminal of the raw material filler is poly-D-lactic acid or poly-L-lactic acid.   The functional filler composition containing the functional filler in any one of Claims 1-5, and the unbonded polylactic acid produced | generated at the time of the said functional filler manufacture. The functional filler according to any one of claims 1 to 5 and polylactic acid which is a matrix polymer,
A resin composition characterized in that at least a part of the polylactic acid interacts with polylactic acid modifying the surface or terminal of the functional filler.   Furthermore, the resin composition of Claim 7 containing the unbonded polylactic acid produced | generated at the time of functional filler manufacture.   The polylactic acid that modifies the surface or the terminal of the functional filler is composed of D-lactic acid or L-lactic acid, and the polylactic acid that is a matrix polymer is composed of an optical isomer of the D-lactic acid or L-lactic acid. Resin composition.   The unbonded polylactic acid produced during the production of the functional filler is composed of D-lactic acid or L-lactic acid, and the matrix polymer polylactic acid is composed of an optical isomer of the D-lactic acid or L-lactic acid. The resin composition as described. It is a manufacturing method of the functional filler in any one of Claims 1-5,
A step of mixing a solution of lactic acid and / or lactide, or a melt of lactic acid and / or lactide and a raw material filler; and polymerizing the lactic acid and / or lactide, so that the surface or terminal of the raw material filler is made of polylactic acid. The manufacturing method of the functional filler characterized by including the process to modify. A method for producing the functional filler composition according to claim 6,
A step of using an excess amount of lactic acid and / or lactide with respect to the raw material filler in mixing the solution of lactic acid and / or lactide or a melt of lactic acid and / or lactide and the raw material filler; and lactic acid and / or The manufacturing method of the functional filler composition characterized by including the process of modifying the surface or terminal of a raw material filler with polylactic acid by polymerizing a lactide. It is a manufacturing method of the resin composition in any one of Claims 7-10,
Mixing a raw material filler with a solution of lactic acid and / or lactide or a melt of lactic acid and / or lactide;
A step of polymerizing lactic acid and / or lactide to modify the surface or terminal of the raw material filler with polylactic acid to form a functional filler; and the functional filler is polylactic acid which is a matrix polymer, and at least one of them And a step of mixing with a part that interacts with polylactic acid that modifies the surface or terminal of the functional filler, a method for producing a resin composition.   The molded object which consists of a resin composition in any one of Claims 7-10.

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