JP2012007039A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition improved in moldability, heat resistance, hydrolysis resistance and abrasion resistance, without emitting a free isocyanate compound affecting working environment in the production or molding processes.SOLUTION: The resin composition includes: a cyclic carbodiimide compound, containing a specific cyclic structure which has one carbodiimide group and in which the first nitrogen and the second nitrogen of the group are bonded by a bonding group, wherein the number of atoms forming the cyclic structure is 8-50; a polyamide; and a polylactic acid.

Description

  The present invention relates to a resin composition, and more particularly to a resin composition having improved moldability, heat resistance, hydrolysis resistance, and wear resistance, and a molded body and fibers obtained from the resin composition.

  In recent years, due to concerns about the depletion of petroleum resources and the problem of increased carbon dioxide in the air that causes global warming, biomass resources that have carbon neutrality that does not rely on petroleum as a raw material and that do not increase carbon dioxide even when burned have been developed. In the polymer field, biomass plastics produced from biomass resources have been actively developed. In particular, polylactic acid has relatively high heat resistance and mechanical properties among biomass plastics, so its use is expanding to tableware, packaging materials, sundries, etc. It has become.

  However, due to its low hydrolysis resistance, polylactic acid is being developed into industrial materials such as electrical / electronic parts and automobile parts, where polycarbonate, polybutylene terephthalate, and polyethylene terephthalate, which are represented by engineering plastics, are used. Not in.

  A technique for improving hydrolysis resistance by blending a stabilizer such as a carbodiimide compound and an antioxidant with respect to polylactic acid has been shown (for example, Patent Documents 1 and 2, etc.). Along with the reaction in which the carbodiimide compound is bonded to the end of the polyester, the compound having an isocyanate group is liberated, generating a unique odor of the isocyanate compound, and deteriorating the working environment.

JP 2008-050584 A JP 2007-056246 A

  The present invention has been made in view of such circumstances, and the object thereof is to produce a free isocyanate compound that deteriorates the working environment in the production or molding process, and the moldability, heat resistance, hydrolysis resistance, The object is to provide a resin composition with improved wear characteristics.

The present inventors have repeatedly studied in order to solve the above-described problems, and have completed the present invention.
That is, the object of the present invention is to
It includes a cyclic structure represented by the following formula (1) in which one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a bonding group, and the number of atoms forming the cyclic structure is 8 to 50 This can be achieved by a resin composition containing a cyclic carbodiimide compound, polyamide and polylactic acid.

  According to the present invention, it is possible to provide a resin composition with improved moldability, heat resistance, hydrolysis resistance, wear resistance, and mechanical properties.

Hereinafter, the present invention will be described in detail.
As polylactic acid in the present invention, any of poly-L-lactic acid, poly-D-lactic acid, or a mixture thereof may be used.
Poly-L-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and 99 to 100 mol% for realizing a high melting point. If the stereocomplex crystallinity described later is given priority. More preferably, it is composed of 95 to 99 mol% of L-lactic acid units. Examples of other units include D-lactic acid units and copolymer component units other than lactic acid. The D-lactic acid unit and the copolymer component unit other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.

  Poly-D-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and 99 to 100 mol% for realizing a high melting point. If the stereocomplex crystallinity described later is given priority. More preferably, it is composed of 95 to 99 mol% of L-lactic acid units. Examples of other units include L-lactic acid units and copolymer component units other than lactic acid. L-lactic acid units and copolymer component units other than lactic acid are 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%.

  The copolymer component unit is a unit derived from dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having a functional group capable of forming two or more ester bonds, and various polyesters, various polyethers composed of these various components, Examples are derived from various polycarbonates and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Polyhydric alcohols include ethylene glycol, propylene glycol, propanediol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and polyteoramethylene glycol. Aliphatic polyhydric alcohols such as aliphatic polyhydric alcohols, and aromatic polyhydric alcohols obtained by adding ethylene oxide to bisphenol. Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, 4-hydroxybenzoic acid and the like. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  Stereocomplex polylactic acid is a mixture of poly-L-lactic acid and poly-D-lactic acid, and can form stereocomplex crystals. Both poly-L-lactic acid and poly-D-lactic acid preferably have a weight average molecular weight of 100,000 to 500,000, more preferably 150,000 to 350,000.

  Poly-L-lactic acid and poly-D-lactic acid can be produced by a known method. For example, L- or D-lactide can be produced by heating and ring-opening polymerization in the presence of a metal polymerization catalyst. Moreover, after crystallizing low molecular weight polylactic acid containing a metal polymerization catalyst, it can be produced by solid phase polymerization by heating under reduced pressure or in an inert gas stream. Further, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence / absence of an organic solvent.

  The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, can be used alone or in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used.

  In the solid phase polymerization method, a relatively low molecular weight lactic acid polyester obtained by the above-described ring-opening polymerization method or lactic acid direct polymerization method is used as a prepolymer. It can be said that the prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature (Tg) or higher and lower than the melting point (Tm) from the viewpoint of preventing fusion. The crystallized prepolymer is filled in a fixed vertical or horizontal reaction vessel, or a reaction vessel (rotary kiln, etc.) where the vessel itself rotates like a tumbler or kiln, and the prepolymer glass transition temperature (Tg) or higher. Heated to a temperature range below the melting point (Tm). There is no problem even if the polymerization temperature is raised stepwise as the polymerization proceeds. In addition, for the purpose of efficiently removing water generated during solid phase polymerization, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

  The polylactic acid of the present invention is a mixture of poly-L-lactic acid and poly-D-lactic acid, and preferably contains a stereocomplex crystal. Here, stereocomplex polylactic acid is formed from poly-L-lactic acid and poly-D-lactic acid, and poly-L-lactic acid and poly-D-lactic acid are L-lactic acid units represented by the following formulas and D-lactic acid. It consists essentially of lactic acid units.

  The weight ratio of poly-L-lactic acid to poly-D-lactic acid in stereocomplex polylactic acid is in the range of 90:10 to 10:90. It is preferably in the range of 75:25 to 25:75, more preferably in the range of 60:40 to 40:60, and preferably as close to 50:50 as possible.

  The weight average molecular weight of the stereocomplex polylactic acid is preferably 100,000 to 500,000. More preferably, it is 100,000-300,000. Here, the weight average molecular weight is a standard polystyrene equivalent weight average molecular weight value measured by gel permeation chromatography (GPC) using chloroform as an eluent.

In the present invention, the stereocomplex crystallinity (S) is defined by the following formula (i).
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(However, ΔHms is the melting enthalpy of the stereocomplex phase crystal obtained from the differential scanning calorimeter (DSC) measurement, ΔHmh is the melting enthalpy of the homophase polylactic acid crystal obtained from the same DSC measurement)

  The stereocomplex crystallinity is preferably 80 to 100%, more preferably 95 to 100%. The stereocomplex polylactic acid referred to in the present invention is preferably 80% of the melting peak attributed to the stereocomplex polylactic acid at 195 ° C. or higher in the melting peak in the temperature rising process in the differential scanning calorimeter (DSC) measurement. Above, more preferably 90% or more, still more preferably 95% or more. The melting point of stereocomplex polylactic acid is in the range of 195 to 250 ° C, more preferably in the range of 200 to 220 ° C. The melting enthalpy is 20 J / g or more, preferably 30 J / g or more. Specifically, in the differential scanning calorimeter (DSC) measurement, the ratio of the melting peak at 195 ° C. or higher in the melting peak in the temperature rising process is 90% or higher, and the melting point is in the range of 195 to 250 ° C. It is preferable that the melting enthalpy is 20 J / g or more.

Stereocomplex polylactic acid can be produced by coexisting and mixing poly-L-lactic acid and poly-D-lactic acid in a predetermined weight ratio.
Mixing can be performed in the presence of a solvent. The solvent is not particularly limited as long as it dissolves poly-L-lactic acid and poly-D-lactic acid. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methyl Pyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, etc., alone or in combination of two or more are preferred.

The mixing can be performed in the absence of a solvent. That is, a method of melting and kneading after mixing a predetermined amount of poly-L-lactic acid and poly-D-lactic acid, and a method of adding and kneading one of them after melting one of them can be employed.
Alternatively, stereoblock polylactic acid in which a poly-L-lactic acid segment and a poly-D-lactic acid segment are bonded can also be suitably used for the polylactic acid of the present invention.
Stereoblock polylactic acid is a block polymer in which a poly-L-lactic acid segment and a poly-D-lactic acid segment are bonded in the molecule.

Such a block polymer is, for example, a method of producing by sequential ring-opening polymerization or a method of polymerizing poly-L-lactic acid and poly-D-lactic acid and then binding them with a chain exchange reaction or a chain extender. The above-mentioned basic methods such as a method of polymerizing poly-L-lactic acid and poly-D-lactic acid, blending and then solid-phase polymerizing to extend the chain, a method of producing from racemic lactide using a stereoselective ring-opening polymerization catalyst, etc. Any block copolymer having a structure can be used regardless of the production method.
However, it is more preferable from the viewpoint of ease of production to use a high-melting stereoblock polymer obtained by sequential ring-opening polymerization and a polymer obtained by a solid phase polymerization method.

  In order to improve the stereocomplex crystallinity, it is preferable to add a specific additive to the polylactic acid used in the present invention. As such an additive, the metal phosphate shown by a following formula can be mentioned as a preferable example.

（式中、Ｒ^１１は水素原子または炭素原子数１〜４のアルキル基を表し、Ｒ^１２及びＲ^１３、同一又は異なっていてもよく、それぞれ水素原子又は炭素原子数１〜１２のアルキル基を表し、Ｍはアルカリ金属原子、アルカリ土類金属、亜鉛原子又はアルミニウム原子を表し、ｎはＭがアルカリ金属原子、アルカリ土類金属原子又は亜鉛原子のときは０を表し、Ｍがアルミニウムのときは１又は２を表す。）

(In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² and R ¹³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M represents an alkali metal atom, an alkaline earth metal, a zinc atom or an aluminum atom; n represents 0 when M is an alkali metal atom, an alkaline earth metal atom or a zinc atom; Represents 1 or 2.)

M is Na, K, Al, Mg, and Ca. In particular, K, Na, and Al can be preferably used.
These metal salts are preferably used in an amount of 10 ppm to 2 wt%, more preferably 50 ppm to 0.5 wt%, still more preferably 100 ppm to 0.3 wt% with respect to polylactic acid. If the amount is too small, the effect of improving the stereocomplex crystallinity is small, and if too large, the resin itself is deteriorated, which is not preferable.

  Moreover, in order to improve the heat resistance of the resin composition, it is preferable to further add calcium silicate. As calcium silicate, what contains a hexagonal crystal can be used, for example, and the one where the particle diameter is low is preferable. For example, when the average primary particle diameter is in the range of 0.2 to 0.05 μm, the resin composition is appropriately dispersed, and thus the heat resistance of the resin composition is good. Further, the addition amount is preferably in the range of 0.01 to 1 wt%, more preferably in the range of 0.05 to 0.5 wt%, based on the resin composition. If the amount is too large, the appearance tends to deteriorate, and if the amount is too small, no particular effect is exhibited, which is not preferable.

The cyclic carbodiimide compound used in the present invention has a cyclic structure. The cyclic carbodiimide compound may have a plurality of cyclic structures.
The cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. For example, when there are a plurality of cyclic structures in the molecule, such as a spiro ring, one cyclic structure bonded to a spiro atom is included in each cyclic structure. Needless to say, the compound may have a plurality of carbodiimide groups as long as it has a carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, and still more preferably 10 to 20.

  Here, the number of atoms in the ring structure means the number of atoms that directly constitute the ring structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably selected in the range of 10-30, more preferably 10-20.

The cyclic structure is preferably a structure represented by the following formula (1).

In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, each of which may contain a hetero atom and a substituent. A heteroatom in this case refers to O, N, S, P. Two of the valences of this linking group are used to form a cyclic structure. When Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.
The linking group may include a heteroatom and a substituent, each having a divalent to tetravalent carbon number of 1 to 20 aliphatic group, a divalent to tetravalent carbon number of 3 to 20 alicyclic group, A linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of combinations include structures such as an alkylene-arylene group in which an alkylene group and an arylene group are bonded.
The linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).

In the formula, Ar ¹ and Ar ² are each independently a 2- to 4-valent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.
As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

R ¹ and R ² each independently contain a heteroatom and a substituent, each having 2 to 4 valent aliphatic groups having 1 to 20 carbon atoms and 2 to 4 valent fatty acids having 3 to 20 carbon atoms A cyclic group, and a combination thereof, or a combination of the aliphatic group, the alicyclic group, and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As cycloalkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group Group, cyclododecane triyl group, cyclohexadecane triyl group and the like. As cycloalkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Yl group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

X ¹ and X ² each independently contain a heteroatom and a substituent, each having a 2 to 4 valent aliphatic group having 1 to 20 carbon atoms and a 2 to 4 valent fatty acid having 3 to 20 carbon atoms It is a cyclic group, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In the formulas (1-1) and (1-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. When s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably selected in the range of 0 to 3. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .

X ³ is a divalent to tetravalent C 1-20 aliphatic group, a divalent to tetravalent C 3-20 alicyclic group, each of which may contain a heteroatom and a substituent, A tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, or an ester group. , Ether group, aldehyde group and the like.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester. Group, ether group, aldehyde group and the like.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups. When Q is a trivalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a trivalent group. When Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a tetravalent group or two are trivalent It is a group.

  Examples of the cyclic carbodiimide used in the present invention include compounds represented by the following formulas (2) to (4).

<Cyclic carbodiimide (2)>

Wherein, Q _a is an aliphatic group, an alicyclic group, an aromatic group or a divalent linking group which is a combination of these, it may contain a heteroatom. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (2), the aliphatic group, alicyclic group, and aromatic group are all divalent. Q _a is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).

In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, these are all divalent.
Examples of the cyclic carbodiimide compound (2) include the following compounds.

<Cyclic carbodiimide (3)>

Wherein, Q _b is an aliphatic group, an alicyclic group, an aromatic group or a trivalent linking group combinations thereof, and may contain a hetero atom. Y is a carrier supporting a cyclic structure. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (3), the inner one of the group constituting the Q _b is trivalent. Q _b is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).

In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are respectively represented by the formulas (1-1) to (1-3). The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, one of these is a trivalent group.
Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3). Examples of the cyclic carbodiimide compound (3) include the following compounds.

<Cyclic carbodiimide (4)>

In the formula, Q _c is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are carriers that support a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.
The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (4), Q _c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups. Q _c is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).

Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are each Ar ^{1 in} formulas (1-1) to (1-3). , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k are the same. Provided that Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² and X _c ³ are one of which is a tetravalent group or two of which are trivalent It is a group.
Z ¹ and Z ² are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding portions, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (4).
Examples of the cyclic carbodiimide compound (4) include the following compounds.

  The above-mentioned cyclic carbodiimide has an unreacted cyclic carbodiimide compound content of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight per 100 parts by weight of polylactic acid. More preferably, it is 0.1 to 1 part by weight.

<Method for producing cyclic carbodiimide compound>
The cyclic carbodiimide compound can be produced by combining conventionally known methods. For example, a method for producing an amine body via an isocyanate body, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body The method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.

  Moreover, the cyclic carbodiimide compound of this invention can be manufactured combining and changing the method described in the following literatures, and an appropriate method can be employ | adopted according to the compound to manufacture.

Tetrahedron Letters, Vol. 34, no. 32, 515-5158, 1993.
Medium- and Large-Membered Rings from Bis (iminophosphoranes): An Efficient Preparation of Cyclic Carbidiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 61, no. 13, 4289-4299, 1996.
New Models for the Study of the Racemization Mechanism of Carbodiimides.
Synthesis and Structure (X-ray Crystallography and 1H NMR) of Cyclic Carbodiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 43, No8, 1944-1946, 1978.
Macrocyclic Ureas As Masked Isocynates, Henri Ulrich et al.
Journal of Organic Chemistry, Vol. 48, no. 10, 1694-1700, 1983.
Synthesis and Reactions of Cyclic Carbodiimides, R.A. Richter et al.
Journal of Organic Chemistry, Vol. 59, no. 24, 7306-7315, 1994.
A New and Efficient Preparation of Cyclic Carboxidimids from Bis (iminophosphoranea) and the System Boc2O / DMAP, Pedro Molina et al.

（２）得られたニトロ体を還元して下記式（ｄ）で表わされるアミン体を得る工程、

（３）得られたアミン体とトリフェニルホスフィンジブロミドを反応させ下記式（ｅ）で表されるトリフェニルホスフィン体を得る工程、および

（４）得られたトリフェニルホスフィン体を反応系中でイソシアネート化した後、直接脱炭酸させることによって製造したものは、本願発明に用いる環状カルボジイミド化合物として好適に用いることができる。
（上記式中、Ａｒ^１およびＡｒ^２は各々独立に、炭素数１〜６のアルキル基またはフェニル基で置換されていてもよい芳香族基である。Ｅ^１およびＥ^２は各々独立に、ハロゲン原子、トルエンスルホニルオキシ基およびメタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、ｐ−ブロモベンゼンスルホニルオキシ基からなる群から選ばれる基である。Ａｒ_ａは、フェニル基である。Ｘは、下記式（ｉ−１）から（ｉ−３）の結合基である。） Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenol represented by the following formula (a-1), nitrophenol represented by the following formula (a-2), and A step of reacting a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c);

(2) A step of reducing the obtained nitro body to obtain an amine body represented by the following formula (d);

(3) a step of reacting the obtained amine body with triphenylphosphine dibromide to obtain a triphenylphosphine body represented by the following formula (e); and

(4) After the obtained triphenylphosphine body is isocyanated in the reaction system and then directly decarboxylated, it can be suitably used as the cyclic carbodiimide compound used in the present invention.
(In the above formula, Ar ¹ and Ar ² are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. E ¹ and E ² are each independently a halogen atom. A group selected from the group consisting of an atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group, Ar _a is a phenyl group, X is represented by the following formula (i -1) to (i-3).

Examples of the polyamide used in the present invention include thermoplastic polymers having amide bonds starting from amino acids, lactams or diamines and dicarboxylic acids.
Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. Examples of lactam include ε-caprolactam and ω-laurolactam.

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

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

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

  Here, since the heat resistance at the time of melt storage of polylactic acid generally tends to deteriorate rapidly when it exceeds 280 ° C., the melting point of the polyamide used in combination with this tends to be 280 ° C. or less. On the other hand, in consideration of the heat resistance of the resin composition, molded body and fiber of the present invention, the melting point of polyamide is preferably 150 ° C. or higher. Considering the above, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 11/6 and copolymer polyamides such as copolymerization of these with polyethylene glycol, mixed Polyamide and polyamide elastomer are preferred.

  The polyamide and polylactic acid can be blended by any method as long as they can be uniformly mixed, such as melt blending or solution blending. In particular, it is preferable to knead in a molten state in a kneader, a single-screw kneader, a twin-screw kneader, a melt reactor, or the like. When the cyclic carbodiimide compound is contained, the polyamide and polylactic acid can be added at the same time when the polyamide and polylactic acid are blended, or can be added to either the polyamide or polylactic acid first and then blended. It may be further added after blending, but at the same time as blending polyamide and polylactic acid, it is added to polylactic acid first, blending with polyamide, and blending with polyamide and polylactic acid. It is preferable to do.

  The kneading temperature may be a temperature at which both resins are melted. However, in consideration of the heat resistance at the time of melting and storing the polylactic acid, the kneading temperature is preferably kneaded within a range of 280 degrees or less.

The mixing ratio of polyamide and polylactic acid may be set so that the polyamide is in the range of 0.5 to 120 parts by weight with respect to 100 parts by weight of polylactic acid, and more preferably 10 to 100 parts by weight. It is particularly preferably 20 to 80 parts by weight.
By setting it as such a mixing ratio, the resin composition excellent in moldability, mechanical characteristics, and heat resistance can be obtained.

  In kneading, it is more preferable to use a compatibilizing agent because the uniformity of the resin is improved and the kneading temperature is lowered. Examples of the compatibilizer include an inorganic filler, a polymer compound obtained by grafting or copolymerizing a glycidyl compound or an acid anhydride, a graft polymer having an aromatic polycarbonate chain, and an organometallic compound. May be used.

  Further, the blending amount of the compatibilizer is preferably 15 wt% to 1 wt%, more preferably 10 wt% to 1 wt%, based on the resin composition, and if less than 1 wt%, the effect as the compatibilizer is small, 15 wt% If it exceeds 50%, the mechanical properties deteriorate, such being undesirable.

  Needless to say, the resin composition of the present invention can be used as it is, but a mold release agent, a surface smoothing agent, a moist heat resistance improving agent, a flame retardant, a filler, a stabilizer (antioxidant, UV absorber). ), Plasticizers, nucleating agents, talc, flakes, elastomers, antistatic agents, rubber-reinforced styrene resins, polyethylene terephthalate, polybutylene terephthalate and polycarbonate.

  Any known release agent may be used. Plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, montan wax, and montanic acid partially saponified ester wax Mineral waxes, paraffin waxes, petroleum waxes such as polyethylene waxes, castor oil and derivatives thereof, and fats and oils waxes such as fatty acids and derivatives thereof, and montanic acid partially saponified ester waxes are particularly preferably used. Among the agents, it is particularly excellent in the effect of improving the high cycle property described later.

Any known surface smoothing agent can be used, and examples thereof include silicone compounds, fluorine surfactants, and organic surfactants.
Any known flame retardant can be used. Specifically, brominated flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants, other An inorganic flame retardant etc. can be mentioned.

  Specific examples of brominated flame retardants include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylene Bistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2,3 -Dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tri (11) bromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenone -A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabrominated bisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A- Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (Tribromoneopentyl) phosphate, poly (pentabromobenzyl polyacrylate), octabromotrimethylphenylindane, dibromoneopentylglycol Cole, pentabromobenzyl polyacrylate, dibromocresyl glycidyl ether, N, N'-ethylene-bis-tetrabromophthalimide and the like. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

Specific examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.
Examples of phosphorus flame retardants include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, and polyphosphates, and red phosphorus.

  Any known filler can be used, for example, silica, mica, calcium carbonate, glass fiber, glass beads, barium sulfate, magnesium hydroxide, wollastonite, calcium silicate fiber, carbon fiber, Examples thereof include magnesium oxysulfate fiber, potassium titanate fiber, titanium oxide, calcium sulfite, white carbon, clay, montmorillonite, and calcium sulfate.

  Any known stabilizer can be used, but lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate , Various metal soap stabilizers such as zinc ricinoleate and zinc stearate, various tantalum stabilizers such as laurate, malate and mercapto, and various lead stabilizers such as lead stearate and tribasic lead sulfate, epoxy Epoxy compounds such as modified vegetable oils, phosphite compounds such as alkylallyl phosphites and trialkyl phosphites, β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, polyols such as sorbitol, mannitol and pentaerythritol, hydrides Examples include talcites and zeolites, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, oxalic anilide ultraviolet absorbers, and hindered amine light stabilizers. .

  As the plasticizer, any known ones can be used. Polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers and An epoxy plasticizer can be used.

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

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

  Specific examples of polycarboxylic acid ester plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate. Trimellitic acid esters such as tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, adipic acid esters such as diisodecyl adipate, n-octyl-n-decyl adipate, triethyl acetylcitrate, tributyl acetylcitrate In addition to citrate esters such as azelaic acid esters such as di-2-ethylhexyl azelate, dibutyl sebacate, and sebacic acid esters such as di-2-ethylhexyl sebacate, Recall) succinate, bis (butyl diglycol) succinate methyl diglycol butyl diglycol succinate, ethyl diglycol butyl diglycol succinate, propyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, methoxycarbonylmethyl methyl Diglycol succinate, ethoxycarbonylmethyl methyl diglycol succinate, benzyl butyl diglycol succinate, bis (methyl diglycol) adipate, bis (butyl diglycol) adipate, methyl diglycol butyl diglycol adipate, ethyl diglycol butyl di Glycol adipate, propyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate Benzylbutyl diglycol adipate, methoxycarbonylmethylmethyl diglycol adipate, methoxycarbonylmethylbutyl diglycol adipate, ethoxycarbonylmethylmethyl diglycol adipate, ethoxycarbonylmethylbutyl diglycol adipate, dimethyldiglycol monobutyldiglycol adipate, benzyldimethyl Diglycol citrate, methoxycarbonyl methyl dimethyl citrate, methoxy carbonyl methyl diethyl citrate, methoxy carbonyl methyl dibutyl citrate, ethoxy carbonyl methyl dimethyl citrate, ethoxy carbonyl methyl dibutyl citrate, ethoxy carbonyl methyl dioctyl citrate, butoxy carbonyl methyl Dimethyl rhino Tray, Butoxycarbonylmethyldiethyl citrate, Butoxycarbonylmethyl dibutyl citrate, Dimethoxycarbonylmethyl monomethyl citrate, Dimethoxycarbonylmethyl monoethyl citrate, Dimethoxycarbonylmethyl monobutyl citrate, Diethoxycarbonylmethyl monomethyl citrate, Diethoxycarbonyl Methyl monobutyl citrate, diethoxycarbonylmethyl monooctyl citrate, dibutoxycarbonylmethyl monomethyl citrate, dibutoxycarbonylmethyl monoethyl citrate, dibutoxycarbonylmethyl monobutyl citrate, ethoxycarbonylmethyldimethyldiglycol citrate, Ethoxycarbonylmethyl dibutyl diglycol cytoley , Diethoxycarbonylmethyl monomethyl diglycol citrate, diethoxycarbonylmethyl monobutyl diglycol citrate, and the like. Among them, methyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, benzyl butyl diglycol Succinate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monobutyl sight Rate, diethoxycarbonylmethyl monobutyl citrate, dibutoxycarboni It may be mentioned methyl monobutyl citrate.

  Examples of the phosphate plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate.

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

  Epoxy plasticizers include epoxy triglycerides composed of alkyl epoxy stearate and soybean oil. In addition, it is also possible to use epoxy resins mainly made of bisphenol A and epichlorohydrin. it can.

  In addition, benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearic acid amide, and aliphatic carboxylic acid esters such as butyl oleate And oxy acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  Any known nucleating agent can be used, and any of inorganic crystal nucleating agents and organic crystal nucleating agents can be used. Specific examples of the inorganic crystal nucleating agent include kaolinite, montmorillonite, synthetic mica, calcium sulfide, boron nitride, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, Calcium oxide, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Amides, ethylenebislauric acid amides, palmitic acid amides, hydroxystearic acid amides, erucic acid amides, carboxylic acid amides such as trimesic acid tris (tert-butylamide), benzylidenesorbitol and its derivatives, sodium-2,2′-methylenebis ( Phosphorus compound metal salts such as 4,6-di-tert-butylphenyl) phosphate, and 2,2-methylbis (4,6-di-tert-butylphenyl) sodium Um etc. can be mentioned.

Any known talc can be used, but it may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. The average particle diameter of talc is preferably 0.1 to 50 μm, more preferably 0.5 to 10 μm.
Any known flakes can be used, and examples thereof include mica, glass flakes, and various metal foils.

  Any known elastomer can be used as the elastomer, but ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, various acrylic rubbers, ethylene-acrylic. Acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid) Butyl copolymer), acid-modified ethylene-propylene copolymer, diene rubber (eg polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (eg styrene-butadiene random copolymer, styrene- Butadiene block copolymer Styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, butadiene- Acrylonitrile copolymer), polyisobutylene, a copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like.

  Any known antistatic agent can be used, but low molecular weight antistatic agents such as anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents. And a polymer type antistatic agent.

  Suitable anionic antistatic agents include sodium alkyl sulfonate, sodium alkyl benzene sulfonate and alkyl phosphate. As the alkyl group, a linear alkyl group having 4 to 20 carbon atoms is preferably used.

  Suitable cationic antistatic agents include phosphonium alkyl sulfonates, phosphonium alkylbenzene sulfonates and quaternary ammonium salt compounds. As the alkyl group, a linear alkyl group having 4 to 20 carbon atoms is preferably used.

  Suitable nonionic antistatic agents include polyoxyethylene derivatives, polyhydric alcohol derivatives, and alkylethanolamines. As the polyoxyethylene derivative, for example, polyethylene glycol having a number average molecular weight of 500 to 100,000 is preferably used.

  Suitable amphoteric antistatic agents include alkylbetaines and sulfobetaine derivatives. Suitable polymeric antistatic agents include polyethylene glycol methacrylate copolymers, polyether amides, polyether ester amides, polyether amide imides, polyalkylene oxide copolymers, polyethylene oxide-epichlorohydrin copolymers and polyether esters. Can be mentioned. These antistatic agents may be used in combination.

  Any known rubber-reinforced styrene-based resin can be used. For example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer).

These additives can be used alone or in combination of two or more kinds depending on the properties to be imparted, and for example, a stabilizer, a release agent and a filler can be added in combination.
Hereinafter, examples of characteristics and combinations to be particularly given will be described.

(1) High cycle performance:
High cycleability means a short injection molding cycle. In improving the high cycle property, for example, a stabilizer, talc, and a release agent may be used in combination.
The addition ratio of the release agent is 0.05 to 3.0 wt% based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of talc is 1 to 10 wt%. That's fine.

(2) Toughness and low temperature impact resistance:
Toughness means tenacity and is an index of resistance to fracture, and is generally evaluated by a Charpy impact test. In improving toughness and low temperature impact resistance, a release agent, a stabilizer and an elastomer may be used in combination, or a release agent, a stabilizer, an elastomer and a polycarbonate may be used in combination.
The addition ratio of the release agent is 0.05 to 3.0 wt% based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the elastomer is 1 to 10 wt%, polycarbonate The addition ratio of may be 1 to 10 wt%.
The resin composition having toughness and low-temperature impact resistance can be suitably used particularly for harness connectors and bumper parts of automobile parts.

(3) Flame retardancy:
In order to improve the flame retardancy, it is only necessary to add a flame retardant, but it is preferable to use a combination of a release agent, a stabilizer, a flame retardant and a filler.
The addition ratio of the flame retardant is 0.05 to 5.0 wt% based on the resin composition, the addition ratio of the release agent is 0.05 to 3.0 wt%, and the addition ratio of the stabilizer is 0.05 to 5 0.0 wt% and the filler addition ratio may be 1 to 10 wt%.

(4) Low warpage:
In improving the low warpage property, a release agent, a stabilizer, flakes and a filler may be used in combination, or a release agent, a stabilizer, a filler and a polycarbonate may be used in combination. In addition, polyethylene terephthalate may be added as an additive to the release agent, stabilizer, filler and polycarbonate.
Further, a release agent, a stabilizer, a filler, and a rubber-reinforced styrene resin may be used in combination.
The addition ratio of the release agent is 0.05 to 3.0 wt% based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, polycarbonate The addition ratio of 1 to 10 wt%, the addition ratio of polyethylene terephthalate may be 1 to 10 wt%, and the addition ratio of rubber-reinforced styrene resin may be 1 to 10 wt%.
A resin composition having good low warpage can be suitably used for household appliances.

(5) Surface appearance:
The surface appearance is composed of surface smoothness and gloss when the resin composition is molded, and is generally determined by touch and visual observation.
In improving the surface appearance, a release agent, a stabilizer, a filler, and polyethylene terephthalate may be used in combination. Further, polycarbonate may be added as an additive to the release agent, stabilizer, filler and polyethylene terephthalate.
The addition ratio of the release agent is 0.05 to 3.0 wt on the basis of the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, and the polycarbonate The addition ratio may be 1 to 10 wt%, and the addition ratio of polybutylene terephthalate may be 1 to 10 wt%.
A resin composition having a high surface appearance can be suitably used for home appliances.

(6) Hydrolysis resistance:
In order to improve the hydrolysis resistance, it is only necessary to add a moist heat resistance improving agent, but it is preferable to use a combination of a mold release agent, a stabilizer, a filler, and a moist heat resistance improving agent.
Furthermore, it is preferable to lower the carboxyl end group concentration of polylactic acid and the carboxyl end group concentration of the aromatic polyester, and the carboxyl end group concentration can be lowered by, for example, a solid phase polymerization reaction.
The addition ratio of the release agent is 0.05 to 3.0 wt on the basis of the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, and the quality resistance The addition ratio of the heat improver may be 0.05 to 5.0 wt%.
The resin composition having high hydrolysis resistance can be suitably used for automobile parts.

(7) Heat shock resistance:
The heat shock property means the degree of durability of the resin when the low temperature holding (about −40 ° C. for about 30 minutes) and the high temperature holding (about 100 ° C. for about 30 minutes) are repeated alternately.
In improving the heat shock resistance, it is preferable to use a combination of a release agent, a stabilizer, a filler, an elastomer, and a heat and heat resistance improver.
The addition ratio of the release agent is 0.05 to 3.0 wt on the basis of the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, the elastomer The addition ratio may be 1 to 10 wt%, and the addition ratio of the heat and heat resistance improver may be 0.05 to 5.0 wt%.
The resin composition having good heat shock resistance can be suitably used for automobile parts.

(8) Tracking resistance:
Tracking resistance evaluates the degree of voltage that causes a permanent carbonized conductive path in a material, and the higher the better.
In improving the tracking resistance, it is preferable to use a combination of a release agent, a stabilizer, a flame retardant, talc and a filler.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the flame retardant is 0.05 to 5.0 wt. %, The addition ratio of talc may be 1 to 10 wt%, and the addition ratio of filler may be 1 to 10 wt%. Resin compositions with good tracking properties can be suitably used for electrical components, particularly relays, switches and the like.

(9) Light resistance:
In order to improve light resistance, it is sufficient to add a stabilizer, but it is preferable to use a combination of a release agent, a stabilizer, a filler, and a flame retardant.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the flame retardant is 0.05 to 5 0.0 wt% and the filler addition ratio may be 1 to 10 wt%.
A resin composition having good light resistance can be suitably used for lighting parts and the like.

(10) Silence:
The quietness means the quietness and vibration damping characteristics when used for a structural material having a noise source, electrical and electronic parts such as housings or relay parts, and a motor case.
In improving the silence, it is preferable to use a combination of a release agent, a stabilizer, an elastomer, talc and a filler.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the elastomer is 1 to 10 wt%, and talc. The addition ratio may be 1 to 10 wt%, and the filler addition ratio may be 1 to 10 wt%.
As described above, the resin composition having good silence can be suitably used for a structural material having a noise source, an electrical / electronic component such as a housing or a relay component, a motor case, or the like.

(11) Low gasity:
Low gasity means that the amount of gas generated when the resin composition is used at a high temperature or for a long period of time is small and the amount of sublimation during melt processing is small.
In improving the low gas property, a release agent, a stabilizer, a flame retardant and a filler may be used in combination, and it is preferable to add a transesterification inhibitor. Examples of the transesterification reaction inhibitor include sodium dihydrogen phosphate, potassium acetate, trimethyl phosphate, and phenylphosphonic acid.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the flame retardant is 0.05 to 5 0.0 wt%, wt%, the filler addition ratio may be 1 to 10 wt%, and the transesterification reaction inhibitor addition ratio may be 0.01 to 5.0 wt%.
The resin composition having a good low gas property can be suitably used for electrical parts, particularly relays and the like.

(12) Antistatic property:
In order to improve the antistatic property, an antistatic agent may be added.
The addition ratio of the antistatic agent may be 0.1 to 10 wt% based on the resin composition.
A resin composition having a good antistatic property can be suitably used, for example, as a wafer carrier used during semiconductor production.

  The resin composition obtained by the present invention can be used as various molded articles and sheets by molding. As a molding method, a conventionally known melt molding resin molding method such as a method of molding after melting or a method of compressing and welding can be used. For example, injection molding, extrusion molding, blow molding, foam molding , Press molding and the like can be suitably used.

  The resin composition obtained by the present invention is excellent in moldability, and particularly when the degree of crystallinity of the molded product is high, the molding shrinkage rate is low and the heat resistance is excellent. In particular, a molded product having a degree of crystallinity exceeding 40% is preferable because of excellent heat resistance.

  In addition, the method for fiberizing the resin composition obtained by the present invention is not particularly limited, but for reasons such as productivity and simplicity of the process, and further, there is no need to use a solvent and the environmental impact is small, etc. It is preferable to fiberize by a melt spinning method.

  The melt spinning conditions may be normal polyester or polyamide melt spinning conditions. That is, a resin composition in which a cyclic carbodiimide compound, polyamide and polylactic acid are mixed is melted by an extruder type or pressure melter type melt extruder, measured by a gear pump, filtered in a pack, and then put into a die. It is discharged as a monofilament, a multifilament, etc. from the provided nozzle.

  The shape of the base and the number of the bases are not particularly limited, and any of circular, irregular, solid, hollow and the like can be adopted. The discharged yarn is immediately cooled and solidified, then bundled, applied with an oil agent, taken up at a spinning speed of 100 to 3000 m / min, wound on a bobbin using a winder, or several hundred to tens of thousands dtex tow. In this state, after the undrawn yarn obtained in a container such as a can is stored, it can be used in a known separate drawing stretcher. In addition, from the viewpoint of improving productivity and simplifying the process, it is possible to employ a direct spinning drawing method in which drawing is continued without winding up the undrawn yarn after spinning.

  The spinning speed is not particularly limited, but if it exceeds 3000 m / min, crystals due to orientation crystallization are generated in the undrawn yarn, and the strength after drawing tends to decrease. This is a preferred mode in many cases, and is selected in the range of 100 to 3000 m / min depending on the equipment, the desired fineness, and the high elongation properties.

  The stretching may be one-stage stretching or multi-stage stretching of two or more stages. From the viewpoint of producing high-strength fibers, the draw ratio is preferably 3 times or more, and more preferably 3 to 10 times. However, if the draw ratio is too high, the fiber is devitrified and whitened, the strength of the fiber is lowered, the elongation at break is too low, and it is not preferable for fiber use. The stretching temperature can be carried out at an arbitrary temperature not lower than the melting point and not lower than the glass transition temperature (Tg) of the used polylactic acid and polyamide, but is preferably 20 to 150 ° C. from the viewpoint of process stability.

  Examples of the preheating method for stretching include a temperature rise of the roll, a liquid heater such as a flat or pin-like contact heater, a non-contact hot plate, and a heat medium bath. When stretching in a liquid bath, the medium used in the liquid bath is water, silicone oil, organic solvents such as ethylene glycol or acetone, inorganic salt solutions such as potassium chloride aqueous solution, supercritical carbon dioxide, etc. In view of contamination of the process and fibers, safety of the work surface, etc., water is most preferable. For the water bath drawing, a hot water bath or the like known as mass production equipment for polyester short fibers can be used. In the case of a water bath, the stretching temperature is 20 to 100 ° C.

  Subsequent to stretching, constant-length heat treatment or relaxation heat shrinkage is performed before winding. The constant-length heat treatment is preferably performed at a temperature equal to or higher than the glass transition temperature (Tg) of the polyester and polyamide and lower than the melting point, specifically 110 to 200 ° C, preferably 120 to 190 ° C. When the constant-length heat treatment temperature is less than 110 ° C., polylactic acid is insufficiently crystallized and physical properties such as strength are insufficient. Further, if the constant-length heat treatment temperature exceeds 200 ° C., a part of the polylactic acid or polyamide used starts to melt, which is not preferable. The relaxation heat treatment is performed at 110 to 165 ° C, preferably 120 to 160 ° C. Similarly, when the heat treatment temperature is less than 130 ° C., the crystallization of polylactic acid is insufficient, and when it exceeds 165 ° C., depending on the polylactic acid or polyamide used, some of the crystals melted by stretching starts, and heat shrinkage and Fiber curing begins.

  The constant-length heat treatment can be performed by contacting the heated yarn with a heated medium or an electric heater with a constant tension applied to the drawn yarn, contact with a roller or contact heater, and superheated high-temperature steam ( There is a non-contact heating method using radiant heat such as a steam or hot air circulation chamber or an infrared heater.

  On the other hand, the relaxation heat treatment includes a method in which the drawn yarn is passed through a hot air circulation chamber, a suction drum through which hot air passes, a heating roller or a contact heater in an overfeed state without tension. As described above, the heating method for the drawn yarn in the constant length heat treatment or the relaxation heat treatment is preferably performed in a dry heat atmosphere or by contact with a dry heat heater.

  In the fiber obtained from the resin composition obtained in the present invention, in the case of producing a short fiber, in addition to the drawing method with a long fiber, a step of cutting with a rotary cutter or the like into a predetermined fiber length according to the application, When crimping is required, a step of applying crimping with an indentation crimper or the like is added between the constant length heat treatment and relaxation heat treatment. At this time, in order to improve crimp imparting property, the fibers before crimping can be preheated with steam, an electric heater or the like.

  The fiber obtained from the resin composition obtained in the present invention can take various fiber structures. Specifically, thread form products such as sewing thread, embroidery thread, string, fabric such as woven fabric, knitted fabric, nonwoven fabric, felt, outer clothing such as shirt, blouson, pants, coat, sweater, uniform, underwear, pantyhose, socks, Lining, interlining, sports clothing, high value-added clothing products such as women's clothing and formal wear, clothing products such as cups and pads, curtains, carpets, chair upholstery, mats, furniture, baskets, furniture upholstery, wall materials, etc. Products for daily use such as belts and slings, as well as various textile products such as canvas, belts, nets, ropes, heavy cloth, bags, industrial materials such as felts and filters, vehicle interior products, and artificial leather products.

  Among the fiber structures as described above, for example, when used as a carpet, false twisting processing and bulky crimp processing are performed on the fibers used, and imparting bulkiness and softness to bring out the texture of the carpet. preferable. Moreover, as a crimp characteristic of the crimped yarn used, it is preferable that the crimp elongation rate after a boiling water process is 3-35%, More preferably, it is 3-25%. This crimp elongation rate is an index of the expression and retention ability of crimp when treated in boiling water in the carpet manufacturing process. By setting this value to 3% or more, heat treatment such as dyeing can be performed. Even if it is applied, the bulkiness of the multifilament yarn is not lowered, and a carpet product rich in bulkiness can be obtained. Further, by setting the crimp elongation rate to 35% or less, it is possible to suppress a decrease in fiber strength and to obtain a carpet product excellent in process passability and use durability.

  Further, when the interior material of the present invention is a carpet, two or three fibers are used, including fibers formed by coating polylactic acid with another thermoplastic resin in consideration of the designability, texture, and touch after tufting. It is good also as the twisted yarn which applied this twist and applied the twist. The number of twists is preferably 50 to 250 times / m from the viewpoint of the design property after tufting, the texture, and the touch, and more preferably 80 to 200 times / m. Moreover, it is preferable to heat-set in order to maintain a form after twisting. The heat setting temperature is preferably 80 to 150 ° C., because the shape stability of the yarn after twisting becomes good, and more preferably 100 to 130 ° C.

  What is necessary is just to employ | adopt suitably the mass per unit area of the tufted pile yarn (weight per unit area) in a carpet according to a use. The abrasion resistance of the carpet is preferably 40% or less, more preferably 30% or less, in the carpet weight loss test (number of revolutions 5500) described later in the examples.

  The fiber obtained from the resin composition of the present invention may be used alone or in combination with other types of fibers. In addition to various combinations with fiber structures composed of other types of fibers, mixed modes include mixed yarns with other fibers, composite false twisted yarns, mixed spun yarns, long and short composite yarns, fluid processed yarns, covering yarns, and twisted yarns. Examples thereof include union, union, pile, pile, mixed cotton, mixed non-woven fabric of long fibers and short fibers, and felt.

  Examples of other fibers to be mixed include cellulose fibers such as cotton, hemp, rayon and tencel, wool, silk, acetate, polyester, polyamide, acrylic, vinylon, polyolefin, polyurethane and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this. In addition, each value in an Example was calculated | required according to the following method.

1) Weight average molecular weight (Mw) (polylactic acid):
The weight average molecular weight of the polymer was determined by GPC (column temperature 40 ° C., chloroform) in comparison with a polystyrene standard sample.

2) Melting point, crystal melting peak, crystal melting start temperature, crystal melting enthalpy measurement (polylactic acid):
TA-2920 differential scanning calorimeter DSC manufactured by TA Instruments was used.
In the measurement, 10 mg of a sample was heated from room temperature to 260 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the first scan, the homocrystal melting peak, homocrystal melting (starting) temperature, homocrystal melting enthalpy and stereocomplex crystal melting peak, stereocomplex crystal melting (starting) temperature and stereocomplex crystal melting enthalpy were determined.

3) DSC measurement of stereocomplex crystallinity [S (%)], crystal melting temperature, etc .:
Using DSC (TA Instrument, TA-2920), the sample was heated to 250 ° C. at 10 ° C./min under a nitrogen stream in the first cycle, and the glass transition temperature (Tg), stereocomplex phase poly Lactic acid crystal melting temperature (Tm *), stereocomplex phase polylactic acid crystal melting enthalpy (ΔHms) and homophase polylactic acid crystal melting enthalpy (ΔHmh) were measured.
In addition, the crystallization start temperature (Tc *) and the crystallization temperature (Tc) were measured by rapidly cooling the measurement sample and then performing a second cycle measurement under the same conditions. The stereocomplex crystallinity is a value obtained by the following formula (ii) from the stereocomplex phase and homophase polylactic acid crystal melting enthalpy obtained by the above measurement.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (ii)
(However, ΔHms is the melting enthalpy of stereocomplex phase crystals, ΔHmh is the melting enthalpy of homophase polylactic acid crystals)

4) Identification of cyclic carbodiimide structure by NMR and determination of cyclic carbodiimide in polyester composition:
The synthesized cyclic carbodiimide compound was confirmed by ¹ H-NMR and ¹³ C-NMR. For NMR, JNR-EX270 manufactured by JEOL Ltd. was used. Deuterated chloroform was used as the solvent.

5) Identification of carbodiimide skeleton of cyclic carbodiimide by IR:
The presence or absence of the carbodiimide skeleton of the synthesized cyclic carbodiimide compound was confirmed by FT-IR at 2100-2200 cm ⁻¹ characteristic of carbodiimide. For FT-IR, Magna-750 manufactured by Thermo Nicolay Co., Ltd. was used.

6) Abrasion resistance:
The sample piece was subjected to a Taber abrasion test method using a H-22 wear wheel, a load of 9.8 N on one wheel and a load of 1000 rotations, the weight of the test piece was measured, and the value obtained by the following formula Was evaluated as “pass” when the wear resistance (%) was less than 5%.
It was.
Abrasion resistance (%) = (mass of test piece before Taber abrasion test (g)-mass of test specimen after Taber abrasion test (g)) / mass of test specimen before Taber abrasion test (g)

7) Hydrolysis resistance:
The reduced viscosity retention rate was evaluated when the sample was treated for 100 hours at 80 ° C. and 95% RH with a thermo-hygrostat.
The hydrolysis resistance is “pass” when the reduced viscosity retention is 80 to less than 90%, “excellent pass” when it is less than 90% to less than 95%, and “particularly pass” when it is between 95% and 100%. To be judged.

8) Presence or absence of generation of isocyanate odor:
When the sample was melted at 260 ° C. for 5 minutes, it was determined by sensory evaluation whether the measurer felt an isocyanate odor. When the isocyanate odor was not felt, it was judged to be acceptable.

9) Good working environment:
Judgment was made based on whether the working environment was deteriorated by the isocyanate odor during the production of the resin composition. When it did not deteriorate, it was evaluated as good.

10) Weight loss of carpet JIS L 1096: 1999 8.17.3 In accordance with the description of the Taber method, H-18 wear wheels are used, and a load of 4.9 N is applied to each pair of left and right wear wheels. After rotating 3000 times and wearing, the decrease in the mass of the fabric was measured.

Hereinafter, the agent used by this invention is described.
The following agents were produced and used as the cyclic carbodiimide compound.

[Production Example 1] Cyclic carbodiimide CC2 (MW = 516)

o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate (0.33mol), _N, N ₂ N- dimethylformamide 200ml in reactor installed with a stirrer and a heating device After charging in an atmosphere and reacting at 130 ° C. for 12 hours, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product D (nitro form).

  Next, intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.

Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirrer, a heating device, and a dropping funnel in an N ₂ atmosphere. A solution prepared by dissolving the intermediate product E (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product F (triphenylphosphine compound).

Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), dichloromethane under N ₂ atmosphere. 150 ml is charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product F (0.025 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, CC2 was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure of CC2 was confirmed by NMR and IR.
Next, the following was synthesized.

[Production Example 2] (Production of poly-L-lactic acid)
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of tin octylate was added, and the reaction was carried out at 180 ° C. in a reactor equipped with a stirring blade in a nitrogen atmosphere. After reacting for 2 hours, the remaining lactide was removed by reducing the pressure and chipped to obtain poly-L-lactic acid.
The obtained poly-L-lactic acid had a weight average molecular weight of 130,000, a glass transition point (Tg) of 63 ° C., and a melting point of 180 ° C.

[Production Example 3] (Production of poly-D-lactic acid)
To 100 parts by weight of D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of octylate was added, and the reaction was carried out at 180 ° C. in a reactor equipped with a stirring blade in a nitrogen atmosphere. After reacting for 2 hours, the remaining lactide was removed by reducing the pressure and chipped to obtain poly-L-lactic acid.
The obtained poly-D-lactic acid had a weight average molecular weight of 130,000, a glass transition point (Tg) of 63 ° C., and a melting point of 180 ° C.

[Production Example 4] (Production of metal phosphate-containing stereocomplex polylactic acid)
The poly-L-lactic acid and poly-D-lactic acid obtained in Production Examples 2 and 3 were weighed out by 50 parts by weight, respectively, and a metal phosphate (“ADEKA STAB” NA-11 manufactured by ADEKA Corporation) 0.5 After thoroughly mixing the chips together with the parts by weight, Laboplast Mill S-15 was kneaded and extruded at a screw temperature of 225 ° C., a strand was taken in a water tank, and chipped with a chip cutter to obtain a stereocomplex resin. The obtained stereocomplex resin was observed to have Mw of 125,000, Tm of 180 ° C. and 220 ° C., and the stereocomplex crystallinity was 95%.

[Example 1]
30 parts by weight of stereocomplex polylactic acid obtained in Production Example 4, 1 part by weight of CC2 obtained in Production Example 1, 70 parts by weight of nylon 6 (melting point: 223 ° C., manufactured by Unitika Ltd.), (Toyo Seiki Seisakusho Co., Ltd.) was used and kneaded at 235 ° C. and a feed rate of 1 kg / hr to obtain a resin composition. The stereocomplex crystallinity of the obtained resin was 92%.
The obtained resin composition was injection-molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded piece. The obtained molded product was white, the stereocomplex crystallinity was 95%, and the appearance was good. Generation of isocyanate odor was not felt during the production of the composition. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. Further, the carboxyl group concentration did not increase even after the stability test against hydrolysis, and the hydrolysis resistance was in the range of “especially excellent”. The wear resistance was “pass”.

[Example 2]
30 parts by weight of the poly-L-lactic acid chip obtained in Production Example 2, 1 part by weight of CC2 obtained in Production Example 1, and 70 parts by weight of nylon 6 (melting point: 223 ° C., manufactured by Unitika Ltd.) chip The mixture was kneaded with an extruder at a kneading temperature of 235 ° C. and supplied to a spinning machine. The spinning temperature in the spinning machine was 230 ° C., and after filtering through a metal nonwoven fabric filter having a mesh size of 20 μm in a spinning pack, the yarn was discharged through a die having a number of holes of 54.
Generation of isocyanate odor was not felt during melt-kneading with an extruder, spinning, or processing. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. Furthermore, the carboxyl group concentration did not increase even after the hydrolysis resistance stability test, and the hydrolysis resistance was in the range of “especially excellent”.

[Reference Example] Use examples of fibers comprising the resin composition of the present invention:
In Example 2, the spun yarn discharged from the die was cooled and solidified with chimney wind, and then a 25% by weight oil solution diluted with low-viscosity mineral oil was applied, and then a take-up roll (Nelson type roll, rotational speed) 700 m / min, roll temperature 65 ° C.).
Subsequently, the first-stage drawing was performed by winding the yarn on a first drawing roll (Nelson type roll, rotation speed 600 m / min, roll temperature 110 ° C.) without winding the yarn. Further, the second stage of stretching was performed by winding on a second stretching roll (Nelson type roll, rotational speed 1800 m / min, roll temperature 150 ° C.) without winding the yarn.
Subsequently, the drawn yarn was guided to a crimping device without being wound up, crimped by heated and compressed air at 170 ° C. and 0.8 MPa, jetted onto a rotary transfer device, and cooled. Next, the plug-like crimped yarn lump was stretched by a pair of separate rolls to break the lump. The crimped yarn was entangled and wound into a cheese shape to obtain a 2000 dtex-94 fil crimped yarn.
The crimped yarn obtained by this operation is subjected to 160 twists / m as an initial twist, two more yarns are combined, 160 twists / m as a top twist, and heat set at 105 ° C. to twist. Got.
Using this twisted yarn, a spunbonded nonwoven fabric having a single fiber fineness of 5.5 dtex per unit area of 100 g / m ² was made from the poly-L-lactic acid chip obtained by the operation of Production Example 2 and used as a base fabric. 1/8 gauge, stitch 6 Tufting was performed at a rate of 8 pieces / mm to obtain a loop carpet having a pile basis weight of 700 g / m ² .
The resulting carpet had a weight loss rate of 3.5% at 300 revolution wear and 33.3% at 5500 revolution wear, indicating good wear resistance.

[Comparative Example 1] A composition containing linear polycarbodiimide (LA-1):
A resin composition was obtained in the same manner as in Example 1 except that the carbodiimide compound was changed to linear carbodiimide LA-1 (manufactured by Nisshinbo Chemical Co., Ltd., “Carbodilite” LA-1). At the time of manufacturing the composition, an isocyanate odor was strongly felt and the working environment was judged to be poor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was unacceptable.

[Comparative Example 2]
In Example 1, the resin composition was obtained similarly except not adding a carbodiimide compound. The wear resistance of the molded article made of the obtained resin composition was “pass”. The reduced viscosity retention rate was “failed”.

[Comparative Example 3]
Example 2 is the same as Example 2 except that nylon 6 is not used and 100 parts by weight of the poly-L-lactic acid chip obtained in Production Example 2 and 1 part by weight of CC2 obtained in Production Example 1 are used. The same operation was performed to obtain a carpet.
The obtained carpet had a weight loss rate of 6.3% at 300 rotation wear and 95.2% at 5500 rotation wear, both of which were inferior to Example 1.

  The resin composition of the present invention is useful as a raw material for various molded articles and fibers.

Claims (13)

It includes a cyclic structure represented by the following formula (1) in which one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a bonding group, and the number of atoms forming the cyclic structure is 8 to 50 A resin composition comprising a cyclic carbodiimide compound, polyamide and polylactic acid.

(In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) The resin composition according to claim 1, wherein Q is a divalent to tetravalent linking group represented by the following formula (1-1), (1-2), or (1-3).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, or combinations thereof, or these aliphatic groups, alicyclic groups and 2 to 4 valent aromatic carbon atoms having 5 to 15 carbon atoms X ¹ and X ² are each independently a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon atom having 3 to 20 alicyclic groups, 2 to 4 A valent aromatic group having 5 to 15 carbon atoms, or a combination thereof, s is an integer of 0 to 10. k is an integer of 0 to 10. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ^2. X ³ is a divalent to tetravalent carbon number. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms having 3 to 20 carbon atoms, an aromatic group having 2 to 4 carbon atoms having 5 to 15 carbon atoms, or a combination thereof, provided that Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R 3 ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups, and when Q is a trivalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ^{One of 2} and X ³ is a trivalent group, and when Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ One of them is a tetravalent group or two are trivalent groups.) The resin composition according to claim 1, wherein the cyclic carbodiimide compound is represented by the following formula (2).

(Wherein Q _a is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) Q _a is represented by the following formula (2-1), (2-2) or a divalent linking group is 3. The resin composition according to the formula (2-3).

(In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. ^{Ar 1, Ar 2, R 1} , R 2, X 1, is the same as ^{X 2,} X ^3, s and k in.) The resin composition according to claim 1, wherein the cyclic carbodiimide compound is represented by the following formula (3).

(Wherein Q _b is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom. Y represents a cyclic structure. It is a carrier to be supported.) Q _b is represented by the following formula (3-1), (3-2) or (3-3) a trivalent linking group is 5. The resin composition according represented by.

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s, and k, with one of these being a trivalent group.)   6. The resin composition according to claim 5, wherein Y is a single bond, a double bond, an atom, an atomic group or a polymer. The resin composition according to claim 1, wherein the cyclic carbodiimide compound is represented by the following formula (4).

(Wherein Q _c is a tetravalent linking group that is an aliphatic group, an aromatic group, an alicyclic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are A carrier carrying a ring structure.) Q _c is represented by the following formula (4-1), (4-2) or (4-3) resin composition according to claim 8 wherein a tetravalent linking group represented by.

(In the formula, Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are respectively represented by formulas (1-1) to (1-3) Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k, provided that one of them is a tetravalent group or two are 3 Valent group.) The resin composition according to claim 8, wherein Z ¹ and Z ² are each independently a single bond, a double bond, an atom, an atomic group or a polymer.   The resin composition according to claim 1, wherein the polylactic acid is a mixture of poly-L-lactic acid and poly-D-lactic acid and contains stereocomplex crystals.   The molded object which consists of a resin composition in any one of Claims 1-11.   The fiber which consists of a resin composition in any one of Claims 1-11.