JP6283464B2 - Eyeglass frame material - Google Patents

Description

  By adding a specific elastomer to a polylactic acid resin having a weight average molecular weight of 100,000 or more, the present invention is excellent in heat resistance and flexibility, has less whitening when bent at room temperature, and has no bleed out skin. The present invention relates to a technique for providing a gentle frame member for eyeglasses.

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 do not depend on petroleum as a raw material and that do not increase carbon dioxide even when burned are formed. In the polymer field, biomass plastics produced from biomass resources are actively developed. In particular, polylactic acid resin has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. It has become like this.
By the way, the stereocomplex polylactic acid resin obtained by mixing the poly-L lactic acid resin and the poly-D lactic acid resin is more resistant to heat than the homo-type polylactic acid resin such as poly-L lactic acid resin and poly-D lactic acid resin. It has excellent characteristics, hydrolysis resistance and crystallization speed.

Patent Document 1 shows a spectacle molded body using a polylactic acid resin. After the molded body is heated and deformed to a temperature higher than the glass transition temperature, it is cooled and deformed into a shape suitable for each person. Has been shown to be possible. However, when the polylactic acid resin is heated to a temperature higher than the glass transition temperature, crystallization is promoted and becomes brittle and hard, which is likely to cause cracks. In addition, the Ude (2a), the ear modern (2b), etc. in FIG. 1 gradually relieve molecular chains in the usage environment and attempt to restore the original shape. For this reason, since it gradually stops fitting to the face, the user himself / herself may adjust the eyeglass frame member to bend and fit the face without heating with a heater or the like. For this reason, flexibility and the property of being difficult to whiten even when bent at room temperature are required.
As a method of imparting flexibility to a polylactic acid resin, a method of adding an elastomer component and a plasticizer is common, but when a plasticizer is added, the plasticizer component gradually bleeds out in the environment of use, causing rashes, etc. Therefore, it is not suitable as a frame member for eyeglasses.

  Patent Document 2 shows a resin composition composed of a polylactic acid resin, which is a biodegradable polymer, an elastomer, and an inorganic filler, and shows that flexibility is imparted. Patent Document 3 describes a polylactic acid composition containing a polyester-based thermoplastic elastomer and shows that impact strength is imparted. However, neither of them shows the effect of bending whitening at room temperature required for the spectacle frame member, nor any knowledge about the glass transition temperature of the elastomer and bending whitening.

Japanese Patent Laid-Open No. 11-43537 JP 2008-63577 A JP 2010-126643 A

  An object of the present invention is to provide a frame member for eyeglasses that is excellent in heat resistance and flexibility, has little whitening when bent at room temperature, and is gentle to the skin without bleeding out.

  As a result of intensive studies to achieve the above object, the present inventors have achieved heat resistance by using a resin composition obtained by adding a specific elastomer to a polylactic acid resin having a weight average molecular weight of 100,000 or more. The present inventors have found that a frame member for eyeglasses that is excellent in flexibility while being maintained, has little whitening when bent at room temperature, and is gentle to the skin without bleeding out, has been completed.

That is, the present invention provides (B) an elastomer (B component) having a glass transition temperature of −30 ° C. or less to 20 to 90 weights per 100 parts by weight of a polylactic acid resin (A component) having a weight average molecular weight of 100,000 or more. Ri Na from the resin composition containing part,
In the tensile test based on ISO527-1 and ISO527-2, the resin composition has an upper yield point, and the ratio of the stress at the upper yield point and the stress at the fracture point represented by the following formula (2) is It is a frame member for spectacles that is 90% or more .
Stress ratio = (breaking stress / yield stress) × 100 (2)
Furthermore, it is preferable that the frame member for spectacles contains 0.01-10 weight part of carbodiimide compounds (C component) with respect to 100 weight part of A component. In addition, 0.01 to 2 parts by weight of at least one antioxidant (D component) selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds and thioether compounds with respect to 100 parts by weight of component A It is preferable to contain.

  The spectacle frame member of the present invention is excellent in heat resistance and flexibility, is less whitened when bent at room temperature, and is gentle to the skin without bleeding out. The frame member for eyeglasses of the present invention can be particularly suitably used as the Ude (2a) and ear modern (2b) member shown in FIG. Addition of 50 to 90 parts by weight of a specific elastomer is more preferable because when used as a spectacle frame member, bending whitening at room temperature does not occur and good quality is obtained.

It is the schematic of the frame member for spectacles manufactured in the Example.

  Hereinafter, each component in the resin composition of the present invention, a blending ratio thereof, a preparation method, and the like will be specifically described sequentially.

<About component A>
As the polylactic acid resin used as the component A in the present invention, any of a poly-L lactic acid resin mainly composed of L-lactic acid units, a poly-D lactic acid resin mainly composed of D-lactic acid units, or a mixture thereof may be used.
The poly-L lactic acid resin (component A-1) and the poly-D lactic acid resin (component A-2) of the present invention substantially comprise an L-lactic acid unit or a D-lactic acid unit represented by the formula (1). .

The optical purity of the poly-L lactic acid resin or poly-D lactic acid resin used in the present invention is preferably 90 to 100 mol%. If the optical purity is lower than this, the crystallinity and melting point of the polylactic acid resin are lowered, and it is difficult to obtain high heat resistance. For this reason, the melting point of the poly-L lactic acid resin or the poly-D lactic acid resin is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and most preferably 175 ° C. or higher. In this respect, the optical purity of lactic acid and lactide of the polymer raw material is preferably 96 to 100 mol%, more preferably 97.5 to 100 mol%, still more preferably 98.5 to 100 mol%, and particularly preferably 99 to 100 mol%. A range of 100 mol% is selected.
The A component includes a poly-L lactic acid resin (A-1 component) containing 90 mol% or more of L-lactic acid units and a poly-D lactic acid resin (A-2 component) containing 90 mol% or more of D-lactic acid units. It is preferable to contain.

Examples of the copolymer unit include a D-lactic acid unit in the case of a poly-L lactic acid resin, an L-lactic acid unit in the case of a poly-D lactic acid resin, and units other than the lactic acid unit. The copolymerization ratio of copolymer units other than lactic acid units is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 2 mol% or less, and most preferably 1 mol% or less.
As copolymerized units, units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, various polyesters composed of these various constituents, various polyethers, 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, 1,3-propanediol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene Examples thereof include aliphatic polyhydric alcohols such as glycol and polypropylene glycol, and aromatic polyhydric alcohols obtained by adding ethylene oxide to bisphenol. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone.

The poly L-lactic acid resin and the poly D-lactic acid resin can be produced by a conventionally known method. For example, L-lactide or D-lactide melt ring-opening polymerization method, low molecular weight polylactic acid resin solid phase weight Examples thereof include a combination method and a direct polymerization method in which lactic acid is subjected to dehydration condensation. The polymerization reaction can be carried out in a conventionally known reaction apparatus. For example, a vertical reactor or a horizontal reactor equipped with a high-viscosity stirring blade 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. In the solid-state polymerization method, it is preferable to crystallize the prepolymer in advance from the viewpoint of preventing fusion of pellets and production efficiency, and the container itself rotates like a fixed vertical or horizontal reaction vessel, or a tumbler or kiln. In a reaction vessel (such as a rotary kiln), the polymerization is carried out at a constant temperature in the temperature range from the glass transition temperature of the prepolymer to less than the melting point, or gradually with the progress of the polymerization. For the purpose of efficiently removing generated water, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used. For melt ring-opening polymerization of lactide, it is preferable to apply a metal-containing catalyst from the viewpoint of production efficiency and polymer quality. From the viewpoint of catalytic activity and side reaction, a catalyst containing tin, preferably a II-valent catalyst, is preferable. Tin compounds, specifically diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate and the like, among others, tin octylate is exemplified as a particularly preferable agent whose safety has been confirmed by FDA. The amount of the catalyst used is preferably 0.1 × 10 ⁻⁴ to 50 × 10 ⁻⁴ mol per kg of lactide, and further considering the reactivity, color tone and stability of the resulting polylactide, 1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ mol is more preferable, and 2 × 10 ⁻⁴ to 15 × 10 ⁻⁴ mol is particularly preferable. Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of the polylactic acid resin. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used. The metal-containing catalyst used at the time of polymerization is preferably deactivated with a conventionally known deactivator prior to use. The deactivator is not particularly limited as long as it is a deactivator generally used as a deactivator for a polymerization catalyst of a polyester resin, but a phosphono fatty acid ester represented by the following general formula (2) is preferable.

In the formula, R _{11 to} R ₁₃ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. Examples of the alkenyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the aryl group include a phenyl group and a naphthalenyl group. R _{11 to} R ₁₃ may be the same or different from each other. N ³¹ is an integer of 1 to 3.

  As the compound represented by the formula (2), ethyl diethylphosphonoacetate, ethyl di-n-propylphosphonoacetate, ethyl di-n-butylphosphonoacetate, ethyl di-n-hexylphosphonoacetate, di-n-octyl Ethyl phosphonoacetate, ethyl di-n-decylphosphonoacetate, ethyl di-n-dodecylphosphonoacetate, ethyl di-n-octadecylphosphonoacetate, ethyl diphenylphosphonoacetate, decyl diethylphosphonoacetate, dodecyl diethylphosphonoacetate , Octadecyl diethylphosphonoacetate, ethyl diethylphosphonopropionate, ethyl di-n-propylphosphonopropionate, ethyl di-n-butylphosphonopropionate, ethyl di-n-hexylphosphonopropionate, di-n -Ethyl octylphosphonopropionate, di-n-decylphosphono Ethyl lopionate, ethyl di-n-dodecylphosphonopropionate, ethyl di-n-octadecylphosphonopropionate, ethyl diphenylphosphonopropionate, decyl diethylphosphonopropionate, dodecyl diethylphosphonopropionate, diethylphosphono Octadecyl propionate, ethyl diethylphosphonobutyrate, ethyl di-n-propylphosphonobutyrate, ethyl di-n-butylphosphonobutyrate, ethyl di-n-hexylphosphonobutyrate, ethyl di-n-octylphosphonobutyrate, di- Ethyl n-decylphosphonobutyrate, ethyl di-n-dodecylphosphonobutyrate, ethyl di-n-octadecylphosphonobutyrate, ethyl diphenylphosphonobutyrate, decyl diethylphosphonobutyrate, dodecyl diethylphosphonobutyrate, octadecyl diethylphosphonobutyrate And the like. In view of efficacy and ease of handling, ethyl diethylphosphonoacetate, ethyl di-n-propylphosphonoacetate, ethyl di-n-butylphosphonoacetate, ethyl di-n-hexylphosphonoacetate, decyl diethylphosphonoacetate, Diethylphosphonoacetic acid octadecyl is preferred.

In the formula (2), when the carbon number of R _{11 to} R ₁₃ is 20 or less, the melting point thereof is lower than the production temperature of the polylactic acid resin or the composition, so that the mixture is sufficiently melt-mixed and efficiently the metal polymerization catalyst. Can be supplemented. The phosphono fatty acid ester has an aliphatic hydrocarbon group between the phosphonic acid diester moiety and the carboxylic acid ester moiety. If n ³¹ is an integer of 1 to 3, it is possible to effectively supplement the metal polymerization catalyst in the polylactic acid resin.
The content of the phosphono fatty acid ester is preferably 0.001 to 0.5 parts by weight, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the polylactic acid resin. If the content of the phosphono fatty acid ester is too small, the deactivation efficiency of the remaining metal polymerization catalyst is extremely poor, and a sufficient effect cannot be obtained. On the other hand, when the amount is too large, contamination of the mold used at the time of molding processing becomes significant. The polymerization deactivator is preferably added at the end of the polymerization, but can be optionally added in each process of extrusion and molding as necessary.

When a mixture of poly L-lactic acid resin (component A-1) and poly D-lactic acid resin (component A-2) is used, the weight ratio (component A-1 / component A-2) is 10:90 to 90: It is preferable to contain in 10 range. The A-1 component / A-2 component is preferably contained in the range of 40:60 to 60:40, more preferably 45:55 to 55:45.
That is, the A component is a poly-L lactic acid resin (A-1 component) containing 90 mol% or more of L-lactic acid units and a poly-D lactic acid resin (A-2 component) containing 90 mol% or more of D-lactic acid units. It is preferable that the weight ratio of A-1 component and A-2 component is the range of 10: 90-90: 10.

  Furthermore, a phosphate ester metal salt represented by the formula (3) and / or (4) is added to a mixture of the poly L-lactic acid resin (A-1 component) and the poly D-lactic acid resin (A-2 component). By containing in a range of preferably 0.01 to 2.0 parts by weight per 100 parts by weight in total of the poly L-lactic acid resin (component A-1) and the poly D-lactic acid resin (component A-2), This is preferable because a polylactic acid resin in which stereocomplex crystals are formed can be obtained. If the phosphate metal salt is less than 0.01 parts by weight, there may be no effect on the formation of stereocomplex crystals and improvement in crystallinity. Decomposition of lactic acid resin component and generation of foreign matter may be caused. From this viewpoint, the application amount of the phosphate ester metal salt is more preferably selected in the range of 0.02 to 1.0 part by weight, and more preferably 0.03 to 1.0 part by weight.

(Wherein _{R 14} is a hydrogen atom or an alkyl group having 1 to 4 carbon _atoms, the R _15, R _{16, R 17} each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,,, _{M 1} Represents an alkali metal atom, alkaline earth metal atom, zinc atom or aluminum atom, p ³² is 1 or 2, q ³² is 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom. In the case of an aluminum atom, 1 or 2 is represented.)

(Wherein _{R 18, R 19} each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,, _{M 2} represents an alkali metal atom, an alkaline earth metal atom, zinc atom or aluminum ^{atom, p 33} Represents 1 or 2, and q ³³ represents 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.
The polylactic acid resin thus produced becomes a stereocomplex polylactic acid resin in which a stereocomplex crystal is highly formed. The polylactic acid resin is formed as follows using the melting enthalpy derived from the polylactic acid resin crystal in the temperature rising process of differential scanning calorimetry (DSC) measurement. The stereocomplex crystallinity represented by formula (1) is preferably 80% or more.
Stereo complex crystallinity = [ΔHms / (ΔHms + ΔHmh)] × 100 (1)
[In the formula (1), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal, which appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]
The ΔHmh and ΔHms were determined by measuring the resin composition using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min.

The higher the stereocomplex crystallinity, the higher the moldability and heat resistance. The stereocomplex crystallinity is preferably 80% or higher, more preferably 85% or higher, and still more preferably 90% or higher. When the stereocomplex crystallinity is lower than 80%, the characteristics of the homopolylactic acid crystal derived from the poly-L lactic acid resin or the poly-D lactic acid resin appear, and the heat resistance becomes insufficient.
The melting point of the stereocomplex polylactic acid resin is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and still more preferably 210 ° C. or higher. When the melting point of the stereocomplex polylactic acid resin is lower than 200 ° C., the heat resistance is insufficient due to its crystallinity and low melting point. The melting enthalpy is preferably 20 J / g or more, more preferably 30 J / g or more. When the melting enthalpy is lower than 20 J / g, the crystallinity is low and the heat resistance is insufficient.
Specifically, it is preferable that the stereocomplex crystallinity is 80% or more, the melting point is 200 ° C. or more, and the melting enthalpy is 20 J / g or more.

  The weight average molecular weight of the polylactic acid resin used in the present invention needs to be 100,000 or more in order to reduce bending whitening at room temperature. Moreover, from a viewpoint of a moldability and mechanical property, 100,000-250,000 are more preferable, and 110,000-200,000 are further more preferable. When the weight average molecular weight is less than 100,000, the polylactic acid resin rapidly becomes brittle, so that fine cracks are generated inside, and it is not only easy to whiten when the molded product is bent at room temperature, but also molded. This may cause the product itself to break. On the other hand, if the weight average molecular weight exceeds 250,000, the flowability during injection molding and the crystallization speed are greatly reduced, and the moldability may deteriorate.

<About B component>
The elastomer used as the component B of the present invention is an elastomer having a glass transition temperature of −30 ° C. or lower. The glass transition temperature is preferably -120 ° C to -35 ° C, more preferably -100 ° C to -40 ° C. When a component with a low glass transition temperature such as an elastomer is included, the entanglement of molecular chains increases. It is less likely to be awakened, and less likely to be whitened. When the glass transition temperature is higher than −30 ° C., there is little entanglement as an elastomer, it is insufficient to suppress whitening, and it is not suitable as a frame member for glasses.
Examples of the elastomer having a glass transition temperature of −30 ° C. or less include polyester elastomer, polyethylene elastomer, polyamide elastomer and the like.

Polyester elastomer is a copolymer of 1,4-butanediol and succinic acid polybutylene succinate (glass transition temperature -32 ° C.), 1,4-butanediol, succinic acid and adipic acid. A polybutylene succinate adipate (glass transition temperature -45 ° C), aliphatic polyester elastomers such as polycaprolactone (glass transition temperature -60 ° C), aromatics with polybutylene terephthalate as the main skeleton and copolymerized glycol components Examples include polyester elastomers. Specifically, Hytrel 4057 (glass transition temperature of −30 ° C.) and Hytrel SC753 (glass transition temperature of −40 ° C.) marketed by Toray DuPont Co., Ltd. under the trade name of Hytrel are exemplified. As the polyester elastomer, an aromatic polyester elastomer is preferably used from the viewpoint of hydrolysis resistance.
The polyethylene elastomer is preferably copolymerized from the viewpoint of compatibility.

  Examples of the elastomer containing a styrene component include a styrene-ethylene-butadiene-styrene copolymer elastomer, a styrene-ethylene-propylene-styrene copolymer elastomer, and a styrene-ethylene-propylene copolymer elastomer. Ethylene-glycidyl methacrylate copolymer elastomer, ethylene-glycidyl methacrylate-methyl acrylate copolymer elastomer, and the like. Examples of the elastomer containing a styrene component include SEPTON 8006 (glass transition temperature of −55 ° C.) marketed by Kuraray Co., Ltd. under the trade name SEPTON, and the elastomer containing an acrylic component is from Sumitomo Chemical Co., Ltd. Examples thereof include Bond First 7L (glass transition temperature-33 ° C.) and Bond First 7M (glass transition temperature-33 ° C.), which are commercially available under the trade name of Bond First.

The polyamide elastomer is an elastomer having a polyamide oligomer as a hard segment and a polyester or polyether ester as a soft segment, such as TPAE-32 (glass transition temperature -40 ° C.) commercially available from T & K TOKA Co., Ltd. Is done.
The above elastomers can be used alone or in combination. In particular, when an ethylene-glycidyl methacrylate copolymer elastomer or an ethylene-glycidyl methacrylate-methyl acrylate copolymer elastomer, which is an elastomer containing an epoxy component, is used in combination with an elastomer component that does not contain an epoxy component, the entanglement of the resin component increases. Thus, bending whitening at room temperature can be reduced, and the amorphous part in the resin component matrix is strengthened by entanglement, and heat resistance is improved, which is preferable. The ratio of the elastomer containing the epoxy component and the elastomer not containing the epoxy component is preferably 10:90 to 50:50, more preferably 20:80 to 50:50.

Content of B component is 20-90 weight part with respect to 100 weight part of A component, 30-90 weight part is preferable and 50-80 weight part is more preferable. If the elastomer content is less than 20 parts by weight, the flexibility is insufficient and whitening tends to occur when bent at room temperature. If the content is more than 90 parts by weight, a significant decrease in heat resistance is observed. Considering the use in a car, it is not suitable as a frame member for glasses.
The ease of bending whitening at room temperature can be determined from the ratio of the stress at the upper yield point and the stress at the breaking point of the SS curve of the tensile test or bending test at room temperature. That is, as the peak of the upper yield point of the SS curve becomes unclear and approaches a flat state, it becomes evidence that the property as an elastomer has been strengthened, and bending whitening at room temperature hardly occurs. That is, in the tensile test based on ISO527-1 and ISO527-2, there is an upper yield point, and the ratio of the stress at the upper yield point and the stress at the break point represented by the following formula (2) is 90% or more. Preferably there is.
Stress ratio = (breaking stress / yield stress) × 100 (2)
The stress ratio is more preferably 95% or more, and most preferably 100% or more. When the stress ratio is less than 90%, the molecular chains in the molded product are not sufficiently entangled, and bending whitening at room temperature may occur easily.

<About component C>
It is preferable that a resin composition contains 0.01-10 weight part of carbodiimide compounds (C component) with respect to 100 weight part of A components. In the present invention, the component C is a carbodiimide compound, and any of a cyclic carbodiimide compound having a cyclic structure and a linear carbodiimide having no cyclic structure can be used.

<Cyclic carbodiimide compound>
The cyclic structure of the cyclic carbodiimide used in the present invention 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. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and most preferably 10 to 15.
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 standpoint of reactivity, there is no particular limitation 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 10-30, more preferably 10-20, and most preferably 10-15.

<Cyclic carbodiimide (1)>
The cyclic structure is a structure represented by the following formula (5).

  In the formula, Q is a divalent to tetravalent linking group represented by the following formula (5-1), (5-2), or (5-3).

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 formulas (5-1) and (5-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. This is because if 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 (5), (7) and (8).

<Cyclic carbodiimide (2)>

  In the formula, Q is a divalent linking group represented by the following formula (6-1), (6-2) or (6-3).

In the formula, Ar _a ¹ (a is a subscript, the same applies hereinafter) and Ar _a ² are each independently a divalent aromatic group having 5 to 15 carbon atoms. R _a ¹ and R _a ² are each independently a divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, and a combination thereof, or these aliphatic groups, It is a combination of an alicyclic group and a divalent aromatic group having 5 to 15 carbon atoms. s _a is an integer of 0. k _a is an integer of 0 to 10. X _a ¹ and X _a ² are each independently a divalent aliphatic group having 1 to 20 carbon atoms, a divalent carbon group having 3 to 20 alicyclic groups, or a divalent aromatic group having 5 to 15 carbon atoms. A group, or a combination thereof. X _a ³ is preferably a divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, a divalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, is there. However, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² and X _a ³ may contain a hetero atom. Examples of the cyclic carbodiimide compound (2) include the following compounds.

<Cyclic carbodiimide (3)>

In the formula, Q _b (b is a subscript, the same applies hereinafter) is a trivalent linking group represented by the following formula (7-1), (7-2) or (7-3), and Y is cyclic. A carrier carrying the structure.

_{^{Wherein, Ar b 1, Ar b 2}} , R b 1, R b 2, X b 1, X b 2, X b 3, s b and k _b are each formula (5-1) to (5-3 ) Are 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 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 (7). Examples of the cyclic carbodiimide compound (7) include the following compounds.

<Cyclic carbodiimide (4)>

In the formula, Q _c (c is a subscript, the same applies hereinafter) is a tetravalent linking group represented by the following formula (8-1), (8-2) or (8-3), and Z ¹ and Z ² is a carrier supporting a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.

Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s _c and k _c are respectively represented by the formulas (5-1) to (5-3): The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. 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 each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding parts, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (8). Examples of the cyclic carbodiimide compound (8) include the following compounds.

<Method for producing cyclic carbodiimide compound>
The cyclic carbodiimide compound can be produced by a conventionally known method. 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 the present invention can be produced by combining and modifying the methods described in the following documents, and an appropriate method can be adopted depending on the compound to be produced.
Tetrahedron Letters, Vol. 34, no. 32, 515-5158, 1993.
Medium- and Large-Membered Rings from Bis (iminophores): An Efficient Preparation of Cyclic Carbidimiides, 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. 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 Boc ₂ O / DMAP, Pedro Molina et al.

  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) What was manufactured by the process of carrying out the direct decarboxylation after isocyanate-izing the obtained triphenylphosphine body in a reaction system can be used suitably as a cyclic carbodiimide compound used for this 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 ₃ is a phenyl group, and X is a group represented by the following formula ( i-1) to (i-3) are linking groups.)

(Where n ^i-1 is an integer of ¹ to 6)

(In the formula, ^mi-2 and ^ni-2 are each independently an integer of 0-3.)

(In the formula, R ^i-3 and R ′ ^i-3 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

  As the linear carbodiimide (including polycarbodiimide compound) used in the present invention, those synthesized by a generally well-known method can be used. For example, an organophosphorus compound or an organometallic compound is used as a catalyst. Examples thereof include those that can be synthesized by subjecting various polyisocyanates to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of about 70 ° C. or higher.

  Examples of the monocarbodiimide compound contained in the carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide and the like. Of these, dicyclohexylcarbodiimide or diisopropylcarbodiimide is preferred from the viewpoint of easy industrial availability. In addition, as the polycarbodiimide compound contained in the carbodiimide compound, those produced by various methods can be used. Basically, conventional polycarbodiimide production methods (US Pat. No. 2,941,956, No. 47-33279, J.0rg.Chem.28, 2069-2075 (1963), Chemical Review 981, Vol.81 No.4, p619-621) can be used.

  Examples of the organic diisocyanate that is a synthetic raw material in the production of the polycarbodiimide compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate. 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, , 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophor Diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. be able to. Moreover, in the case of the said polycarbodiimide compound, it can also control to a suitable polymerization degree using the compound which reacts with the terminal isocyanate of polycarbodiimide compound, such as monoisocyanate. Examples of the monoisocyanate for sealing the end of such a polycarbodiimide compound and controlling the degree of polymerization thereof include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like. be able to.

As a specific degree of carboxyl group terminal blocking, the concentration of the carboxyl group terminal of the polylactic acid resin is preferably 10 equivalents / 10 ³ kg or less from the viewpoint of improving hydrolysis resistance, and 6 equivalents / 10 ³ kg or less. More preferably it is.
The content of component C is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and still more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of component A. It is. If the content is less than 0.01 parts by weight, the amount of the end-capping agent added to the carboxyl terminal is too small, and sufficient hydrolysis resistance may not be obtained. Fluidity may be significantly reduced.

<About D component>
In the present invention, the resin composition contains at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds as an antioxidant (component D). Can be used. By blending an antioxidant (component D), not only the hue and fluidity during molding are stabilized, but also effective in improving hydrolysis resistance.

  Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate. 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebi (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) ) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- ( -Tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) ), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) 4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. Particularly preferred is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. All of these are readily available. The said hindered phenol type compound can be used individually or in combination of 2 or more types.

  Phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) ) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentae Thritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite. Furthermore, as other phosphite compounds, those that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and the like. Suitable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl). Phenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.

  Also, for example, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine [commercially available as “Sumilyzer GP” (manufactured by Sumitomo Chemical Co., Ltd.). 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine And so on.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenyl phosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenyl phosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. The phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and stabilizers based on the phosphonite are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) is commercially available and any of them can be used. The said phosphonite type compound can be used individually or in combination of 2 or more types.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like. The said thioether type compound can be used individually or in combination of 2 or more types.

  The content of component D is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of component A. . When the blending amount is less than 0.01 parts by weight, the antioxidant effect is insufficient, and not only the hue and fluidity during molding are unstable, but also hydrolysis resistance may be deteriorated. Moreover, when there are more this compounding quantities than 2 weight part, the reaction component derived from antioxidant, etc. may be changed, and hydrolysis resistance may be deteriorated.

  Further, it is preferable to use a combination of one or more of the hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds. By using a combination of one or more of hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds, a synergistic effect as a stabilizer is exhibited, and hue and flow during molding are further improved. It is effective in stabilizing the properties and improving the hydrolysis resistance.

<About other ingredients>
<Hydrotalcite>
In the present invention, hydrotalcite can be included. The hydrotalcite used in the present invention is preferably a synthetic hydrotalcite represented by the following formula (9).

(Expressed M ²⁺ is magnesium ions in the formula, the divalent metal ions such as zinc ion, N ³⁺ is aluminum ions, trivalent metal ions such as chromium ions, A ^n-is an n-valent interlayer anion, x Is 0 <x ≦ 0.33, m is 0 ≦ m <2, and n is an integer of 1 ≦ n ≦ 5.)
[M ²⁺ _1-X N ³⁺ _x (OH) ₂ ] in the formula (9) is a hydroxide sheet, which is formed by the fact that octahedrons formed by surrounding six OHs with metal ions share each other. . The hydroxide sheets overlap to form a layered structure. [A ⁿ⁻ _{x / n} · mH ₂ O] in the formula (9) represents an n-valent anion and water of crystallization entering between the hydroxide sheets.
M ²⁺ is not particularly limited as long as it is a divalent metal ion, but generally magnesium ion is preferably used. Further, N ³⁺ is not particularly limited as long as it is a trivalent metal ion, typically aluminum ions are preferably used are in, A ^n-is are preferably used carbonate ions.
Although the mechanism by which hydrotalcite improves the hydrolysis resistance of polylactic acid resin is not clear, it is necessary to adsorb acid that acts as a catalyst for the hydrolysis reaction of polylactic acid resin, such as lactic acid generated by thermal decomposition and hydrolysis. Conceivable.

The hydrotalcite used in the present invention is preferably dehydrated by firing. The temperature for the baking treatment can be arbitrarily selected according to the chemical structure of the hydrotalcite. For ^{example, M 2+} is magnesium ^{ion, N 3+} is aluminum ^{ion, A n-carbonate} ions, magnesium ions: aluminum ion = 2: 1 (x = 0.33 ) if it was, dehydration temperature of crystal water is Since it is 210 ° C., it can be dehydrated by baking at or above this temperature. As x becomes smaller than 0.33, the dehydration temperature of crystal water becomes lower. By using hydrotalcite that has been subjected to dehydration treatment, it is possible to prevent the resin from being decomposed in a process such as extrusion or molding, and thus a resin composition having more excellent hydrolysis resistance can be obtained. Therefore, the range of m in Formula (9) is preferably 0 ≦ m <0.5, and most preferably 0 ≦ m <0.1.

  Moreover, it is preferable that the hydrotalcite used by this invention is surface-treated. Examples of the surface treatment agent include silane coupling agents, titanate coupling agents, silicone compounds, fatty acids, fatty acid salts, synthetic resins, and particularly, fatty acids and fatty acid salts that are familiar with polylactic acid resins are preferably used. Surface treatment of hydrotalcite not only prevents the degradation of polylactic acid resin in processes such as extrusion and molding, but also increases dispersion of hydrotalcite in polylactic acid resin, effectively Thus, a resin composition with better hydrolysis resistance can be obtained.

  The fatty acid used for the surface treatment is not particularly limited as long as it is a fatty acid, but a higher fatty acid having a relatively high boiling point and having 12 or more carbon atoms is preferable. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like. The fatty acid salt used for the surface treatment is not particularly limited as long as it is a fatty acid salt, but a higher fatty acid salt having a relatively high boiling point and having 12 or more carbon atoms is preferable. Specific examples include laurate, myristate, palmitate, stearate, oleate, linoleate, and linolenate. As the salt used in the higher fatty acid salt, inorganic compounds such as sodium, potassium and zinc are preferable.

In the present invention, any of hydrotalcite that has been either dehydrated or untreated, hydrotalcite that has been subjected to dehydration or surface treatment, or hydrotalcite that has been subjected to both dehydration or surface treatment may be used. Preferably, hydrotalcite subjected to either dehydration treatment or surface treatment, more preferably hydrotalcite subjected to both dehydration treatment or surface treatment, can be used.
DHT-6 (manufactured by Kyowa Chemical Industry Co., Ltd.) is a hydrotalcite that has not been subjected to dehydration or surface treatment, and DHT-4C (Kyowa Chemical Industry Co., Ltd.) is a hydrotalcite that has only been dehydrated. ), As hydrotalcite that is only surface-treated, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.), as hydrotalcite that is both dehydrated and surface-treated, DHT-4A-2 (Manufactured by Kyowa Chemical Industry Co., Ltd.) can be obtained as commercial products.
The amount of hydrotalcite added is preferably 0.01 to 0.3 parts by weight, more preferably 0.03 to 0.2 parts by weight, and 0.05 to 0.2 parts by weight with respect to 100 parts by weight of component A. Is most preferred. If the amount of hydrotalcite added is less than 0.01 parts by weight, the effect of improving the hydrolysis resistance cannot be obtained. If the amount of hydrotalcite added exceeds 0.3 parts by weight, the polylactic acid resin may be thermally decomposed. This may cause the hydrolysis resistance to deteriorate.

<Light stabilizer>
In the present invention, the resin composition may contain a light stabilizer. Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.

  Examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′. -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2 - carboxy benzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl - acryloxy-isopropoxyphenyl) benzophenone.

  Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (Α, α-Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α Dimethylbenzyl) phenyl] -2H- benzotriazole, 2- (4'-octoxy-2'-hydroxyphenyl) benzotriazole.

Examples of the aromatic benzoate compounds include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.
Examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.
Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-cyano-3,3′-diphenyl acrylate.

Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, Bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidylo Cis) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid And 1, 2, 2, 6 Condensation product of 6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol Etc.
The content of the light stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the component A.

<Crystallization accelerator>
In the present invention, the resin composition may contain a crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
In other words, the application of the crystallization accelerator improves the moldability and crystallinity of the polylactic acid resin (component A), and crystallizes sufficiently even in normal injection molding to obtain a molded product excellent in heat resistance and moist heat resistance. be able to. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.
As the crystallization accelerator, either an inorganic crystallization nucleating agent or an organic crystallization nucleating agent can be used.

  As inorganic crystallization nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like. These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned.

Also, organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Of propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid resin, sodium salt of ethylene-acrylic acid copolymer, styrene-maleic anhydride copolymer Examples thereof include sodium salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.
Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization nucleating agent may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the component A.

<Organic filler>
In the present invention, the resin composition can contain an organic filler. By containing an organic filler, a resin composition excellent in mechanical properties, heat resistance and moldability can be obtained.
Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes. The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.
Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.
In the present invention, the content of the organic filler is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, and further preferably 10 to 10 parts by weight with respect to 100 parts by weight of the component A from the viewpoint of moldability and heat resistance. 150 parts by weight, particularly preferably 15 to 100 parts by weight.

<Release agent>
In the present invention, the resin composition may contain a release agent. Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid resin molded product having excellent mechanical properties, moldability, and heat resistance can be obtained.

Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like.
Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.

As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.
Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.

  Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, and polypropylene glycol fatty acid esters.

Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and montanic acid partial saponified ester and ethylene bisstearic acid amide are particularly preferable. .
A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, with respect to 100 parts by weight of component A.

<Antistatic agent>
In the present invention, the resin composition may contain an antistatic agent. Examples of the antistatic agent include quaternary ammonium salt compounds such as (β-lauramidopropionyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.
One type of antistatic agent may be used, or two or more types may be used in combination. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the component A.

<Others>
Moreover, in this invention, in the range which is not contrary to the meaning of this invention, thermosetting resins, such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, and an epoxy resin, polycarbonate resin, glass transition temperature is -30 degreeC. Higher polyester resin, polyarylate resin, liquid crystalline polyester resin, polyamide resin having a glass transition temperature higher than −30 ° C., polyimide resin, polyetherimide resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polystyrene resin, acrylonitrile / A thermoplastic resin such as a styrene copolymer (AS resin), a polystyrene resin, a high-impact polystyrene resin, or a syndiotactic polystyrene resin may be included. Colorants containing organic and inorganic dyes and pigments, for example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, and chromium such as zinc chromate Contains acid salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. You may let them. Also, nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red, chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue In addition, additives such as slidability improvers such as graphite and fluorine resin may be added. These additives can be used alone or in combination of two or more.

<About the manufacturing method of a resin composition>
i) Preparation of Coexisting Composition In the present invention, when a mixture of poly-L lactic acid resin (A-1 component) and poly-D lactic acid resin (A-2 component) is used as the polylactic acid resin (A component), other Before melt-mixing with the additive component of the phosphoric acid ester metal salt represented by formula (3) and / or formula (4), poly-L lactic acid resin (component A-1) and poly-D lactic acid resin (A -2 component) is preferably allowed to coexist in advance. As a method of coexistence, a method of mixing the poly-L lactic acid resin (A-1 component) and the poly-D lactic acid resin (A-2 component) as uniformly as possible, This is preferable because it can be generated efficiently. The coexisting composition can be prepared by any method as long as they are uniformly mixed when heat-treated. The method is carried out in the presence of a solvent, or the method is carried out in the absence of a solvent. Etc. are exemplified.
Methods for preparing the coexisting composition in the presence of a solvent include a method of obtaining the coexisting composition by reprecipitation from a state dissolved in a solution, and a method of obtaining the coexisting composition by removing the solvent by heating. Preferably mentioned.

  In the case of obtaining such a coexisting composition by reprecipitation in the presence of a solvent, first, coexistence of a poly-L lactic acid resin (A-1 component) and a poly-D lactic acid resin (A-2 component) The composition is prepared by reprecipitation. Here, the A-1 component and the A-2 component are preferably carried out by adjusting and mixing separately dissolved solutions in a solvent, or by dissolving and mixing both in a solvent together. Here, the weight ratio (A-1 component / A-2 component) between the poly-L lactic acid resin (A-1 component) and the poly-D lactic acid resin (A-2 component) is 10/90 to 90 / It is preferable to prepare so that it may become the range of 10 in order to produce | generate the stereocomplex crystal | crystallization of polylactic acid resin (A-1 component, A-2 component) efficiently in a resin composition. The weight ratio of the A-1 component to the A-2 component is more preferably 25/75 to 75/25, particularly preferably 40/60 to 60/40. Although a solvent will not be specifically limited if polylactic acid resin (A-1 component, A-2 component) melt | dissolves, For example, chloroform, a methylene chloride, a dichloroethane, tetrachloroethane, a phenol, tetrahydrofuran, N -Methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol or the like, or a mixture of two or more of them is preferred.

  The phosphate ester metal salt represented by the formula (3) or the formula (4) is insoluble in the above solvent or may remain in the solvent after reprecipitation even when dissolved in the solvent. The polylactic acid resin (A-1 component, A-2 component) mixture obtained by the above and the phosphate ester metal salt represented by formula (3) or formula (4) are separately mixed to prepare a coexisting composition. There is a need. In the method of obtaining a coexisting composition of a polylactic acid resin (A-1 component, A-2 component) mixture and a phosphoric acid ester metal salt represented by formula (3) or formula (4), they are uniformly mixed. The method is not particularly limited, and any method such as powder mixing or melt mixing can be used.

  Next, coexistence of the polylactic acid resin (component A-1 and component A-2) and the phosphate ester metal salt represented by formula (3) or formula (4) by removing the solvent from the presence of the solvent When preparing the composition at once, the A-1 component and the A-2 component, and the phosphoric acid ester metal salt represented by the formula (3) or the formula (4) are separately dissolved or dispersed in a solvent. The dispersion can be prepared and mixed, or the dispersion can be prepared by mixing or dissolving all components together in a solvent and mixed, and then the solvent is evaporated by heating. The solvent is not particularly limited as long as it dissolves the polylactic acid resin (component A-1, component A-2) and the phosphate metal salt represented by formula (3) or formula (4). However, for example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, or a mixture of two or more of them is preferable. . The rate of temperature increase after evaporation of the solvent (heat treatment) is preferably, but not limited to, a short time since there is a possibility of decomposition when heat treatment is performed for a long time.

  The preparation of the coexisting composition of the polylactic acid resin (A-1 component, A-2 component) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) can be performed even in the absence of a solvent. it can. That is, the A-1 component and the A-2 component, which have been powdered or chipped in advance, and the phosphoric acid ester metal salt represented by the formula (3) or the formula (4) are mixed in a predetermined amount and then melted and mixed. Or a method in which any one of the A-1 component and the A-2 component is melted and then the remaining components are added and mixed. Here, the size of the powder or chip is not particularly limited as long as the powder or chip of each polylactic acid unit (A-1 component, A-2 component) is uniformly mixed. The following is preferable, and the size is preferably 1 to 0.25 mm. When melting and mixing, a stereocomplex crystal is formed regardless of the size. However, when the powder or chip is simply melted after being uniformly mixed, if the diameter of the powder or chip becomes more than 3 mm, the mixture is mixed. Is not preferable, and homopolylactic acid crystals are likely to precipitate. In addition, as a mixing device used to uniformly mix the above powder or chips, in the case of mixing by melting, in addition to a reactor with a batch type stirring blade, a continuous reactor, a biaxial or uniaxial In the case of mixing with an extruder or powder, a tumbler type powder mixer, a continuous powder mixer, various milling devices, or the like can be suitably used.

  Furthermore, when preparing such a co-existing composition, elastomer (B component), carbodiimide compound (C component), antioxidant (D component), and other additives, hydrotalcite, inorganic filler breakage suppression Agent, lubricant, ultraviolet absorber, light stabilizer, mold release agent, flow modifier, colorant, light diffusing agent, fluorescent whitening agent, phosphorescent pigment, fluorescent dye, antistatic agent, antibacterial agent, crystal nucleating agent, etc. Various additives can be allowed to coexist.

  In particular, the addition of a carbodiimide compound (component C) at the stage of preparation of the coexisting composition means that the end blocker and the polylactic acid resin (component A) are mixed more uniformly, and the acidity of the polylactic acid resin is increased. Since the terminal is blocked more efficiently, it is preferable for improving the hydrolysis resistance of the obtained final resin composition. In addition, it is possible to add an antioxidant such as a hindered phenol compound, a phosphite compound, a phosphonite compound, or a thioether compound at the stage of preparing the coexisting composition, It is particularly preferable for improving the thermal stability.

ii) Heat treatment of coexisting composition In the present invention, when a mixture of poly-L lactic acid resin (A-1 component) and poly-D lactic acid resin (A-2 component) is used as polylactic acid resin (A component), other Before melt-mixing with the additive component, the coexisting composition of the polylactic acid resin (A-1 component, A-2 component) and the phosphate ester metal salt represented by formula (3) or formula (4) is heat-treated. Is preferred. Such heat treatment refers to holding the composition in a temperature range of 240 to 300 ° C. for a certain period of time. The temperature of the heat treatment is preferably 250 to 300 ° C, more preferably 260 to 290 ° C. If it exceeds 300 ° C., it is difficult to suppress the decomposition reaction, which is not preferable, and if it is less than 240 ° C., uniform mixing by heat treatment does not proceed, and stereocomplex crystals are not easily generated efficiently. The heat treatment time is not particularly limited, but is 0.2 to 60 minutes, preferably 1 to 20 minutes. As an atmosphere during the heat treatment, either an inert atmosphere at normal pressure or a reduced pressure can be applied. As the apparatus and method used for the heat treatment, any apparatus and method that can be heated while adjusting the atmosphere can be used. For example, a batch type reactor, a continuous type reactor, a biaxial or uniaxial type can be used. It is also possible to adopt a method of processing while forming using an extruder or the like, or a press machine or a flow tube type extruder. Here, the preparation of the coexisting composition of the polylactic acid resin (component A-1, component A-2) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) is carried out in the absence of a solvent. In the case of carrying out by the melt mixing method, heat treatment of the coexisting composition can be achieved simultaneously with the preparation of the coexisting composition.

iii) Preparation of resin composition In the present invention, the resin composition comprises a polylactic acid resin (component A) (including the heat-treated coexisting composition), an elastomer (component B), a carbodiimide compound (component C), and an antioxidant. (D component), and other additive components are produced by mixing (however, the components contained in the coexisting composition are excluded).
Other additive components include hydrotalcite, inorganic filler breakage inhibitor, lubricant, UV absorber, light stabilizer, mold release agent, flow modifier, colorant, light diffusing agent, fluorescent whitening agent, phosphorescent Arbitrary additive components such as pigments, fluorescent dyes, antistatic agents, antibacterial agents, crystal nucleating agents and the like can be mentioned.

  In order to produce such a resin composition, any method is adopted. For example, a method of premixing polylactic acid resin (component A) and other components, then melt-kneading and pelletizing can be mentioned. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed.

<Manufacture of eyeglass frame members>
The spectacle frame member can be manufactured by using various molding methods such as injection molding and extrusion molding using the pellets manufactured by the above method as a raw material. That is, the present invention includes a frame member for eyeglasses produced by bending a molded product formed by injection molding, extrusion molding, thermoforming, blow molding or foam molding. The frame member for spectacles is preferably Ude or ear modern.

In the injection molding, not only a normal cold runner molding method but also a hot runner molding method is possible. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known.
In extrusion molding, a desired shape can be obtained by cutting out from various shaped extruded products, sheets, films and the like into the shape of a frame member for spectacles. Moreover, it is also possible to obtain a hollow molded product by subjecting it to rotational molding or blow molding.
When the molded product obtained above is subjected to a hot bending process, the processed part is heated to a temperature higher than the glass transition temperature and lower than the melting point of the resin composition. The heating method is not particularly limited, and examples thereof include heating with an electronic heater, a light, a hot air blower, or the like. Then, it may be heated locally only to the resin or the entire structure may be heated, and the heating method and the like are not particularly limited as long as at least the processing site is in the temperature range. Since the bending in the softened state can be performed by heating in the temperature range, it is possible to perform processing while preventing cracks and the like.

  Furthermore, the frame member for spectacles of the present invention can be provided with other functions by surface modification. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for normal resin molded products can be applied.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.

1. Manufacture of polylactic acid resin Polylactic acid resin was manufactured by the method shown in the following manufacture example. Moreover, each value in a manufacture example was calculated | required with the following method.
(1) Polymer weight average molecular weight (Mw)
It was measured by gel permeation chromatography (GPC) and converted to standard polystyrene. The GPC measurement instrument used a differential refractometer Shimadzu RID-6A as a detector and Toso-TSKgel G3000HXL as a column. The measurement was performed by injecting 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) at a temperature of 40 ° C. and a flow rate of 1.0 ml / min using chloroform as an eluent.
(2) Carboxyl group concentration The sample was dissolved in purified o-cresol under a nitrogen stream, and then titrated with 0.05 N potassium hydroxide in ethanol using bromocresol blue as an indicator.
(3) Stereocomplex crystallinity The stereocomplex from the following formula (1) using the melting enthalpy derived from the polylactic acid resin (component A) crystal in the heating process of DSC (TA-2920 manufactured by TA Instruments). The crystallinity parameter was evaluated.
Stereo complex crystallinity = [ΔHms / (ΔHms + ΔHmh)] × 100 (1)
[In the formula (1), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal, which appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]
The ΔHmh and ΔHms were determined by measuring the resin composition using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min.
In the examples and comparative examples of the present invention, the following materials were used.

[A-1 component: poly L-lactic acid resin (PLLA)]
[Production Example 1-1]
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 reactor was stirred at 180 ° C. in a nitrogen atmosphere with a stirring blade. For 2 hours, 1.2 times equivalent of phosphoric acid to tin octylate was added, and then the remaining lactide at 13.3 Pa was removed and pelletized to obtain poly L-lactic acid resin (A-1). . The resulting poly L-lactic acid resin has a weight average molecular weight of 152,000, a melting enthalpy (ΔHmh) of 49 J / g, a melting point (Tmh) of 175 ° C., a glass transition point (Tg) of 55 ° C., and a carboxyl group content of 14 eq / ton.

[Component A-2: Production of poly-D-lactic acid resin (PDLA)]
[Production Example 1-2]
Poly D-lactic acid was prepared in the same manner as in Production Example 1-1 except that D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) was used instead of L-lactide in Production Example 1-1. Resin (A-2) was obtained. The resulting poly-D-lactic acid resin has a weight average molecular weight of 151,000, a melting enthalpy (ΔHmh) of 48 J / g, a melting point (Tmh) of 175 ° C., a glass transition point (Tg) of 55 ° C., and a carboxyl group content of It was 15 eq / ton.

[Component A-3: Production of stereocomplex polylactic acid resin (scPLA)]
[Production Example 1-3]
100 parts by weight of polylactic acid resin composed of 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-2 and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) ) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [manufactured by Nippon Steel Works, Ltd. TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 250 rpm, a discharge rate of 9 kg / h, and a vent vacuum of 3 kPa to obtain a stereocomplex polylactic acid resin (A-3). The resulting stereocomplex polylactic acid resin had a weight average molecular weight of 130,000, a melting enthalpy (ΔHms) of 56 J / g, a melting point (Tms) of 220 ° C., a glass transition point (Tg) of 58 ° C., and a carboxyl group content of 17 eq / The stereocomplex crystallinity calculated using ton and formula (1) was 100%.

[Component A-4: Production of stereocomplex polylactic acid resin (scPLA)]
[Production Example 1-4]
100 parts by weight of polylactic acid resin composed of 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-2 and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) ) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [manufactured by Nippon Steel Works, Ltd. TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 280 ° C., a screw rotational speed of 250 rpm, a discharge rate of 8 kg / h, and a vent vacuum of 3 kPa to obtain a stereocomplex polylactic acid resin (A-4). The resulting stereocomplex polylactic acid resin has a weight average molecular weight of 105,000, a melting enthalpy (ΔHms) of 59 J / g, a melting point (Tms) of 217 ° C., a glass transition point (Tg) of 57 ° C., and a carboxyl group content of The stereocomplex crystallinity calculated using 23 eq / ton and formula (1) was 100%.

[A′-1 Component: Production of Stereo Complex Polylactic Acid Resin (scPLA)]
[Production Example 1-5]
100 parts by weight of polylactic acid resin composed of 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-2 and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) ) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [manufactured by Nippon Steel Works, Ltd. TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 290 ° C., a screw rotation speed of 250 rpm, a discharge rate of 5 kg / h, and a vent vacuum of 3 kPa to obtain a stereocomplex polylactic acid resin (A′-1). The resulting stereocomplex polylactic acid resin had a weight average molecular weight of 92,000, a melting enthalpy (ΔHms) of 59 J / g, a melting point (Tms) of 214 ° C., a glass transition point (Tg) of 56 ° C., and a carboxyl group content of The stereocomplex crystallinity calculated using 29 eq / ton and formula (1) was 100%.
The results are summarized in Table 1. In Table 1, ΔHms is the melting enthalpy of the crystalline melting point appearing at 190 ° C. or higher and lower than 250 ° C., and ΔHmh is the melting enthalpy of the crystalline melting point appearing below 190 ° C. Tms is a crystalline melting point appearing at 190 ° C. or more and less than 250 ° C., and Tmh is a crystalline melting point appearing at less than 190 ° C.

2. Production of cyclic carbodiimide Cyclic carbodiimide was produced by the method shown in the following production examples. Moreover, each value in a manufacture example was calculated | required with the following method.
(1) Identification of cyclic carbodiimide structure by NMR Identification of the synthesized cyclic carbodiimide compound by NMR was confirmed by ¹ H-NMR and ¹³ C-NMR using JNR-EX270 manufactured by JEOL Ltd. In addition, deuterated chloroform was used as a solvent.
(2) Identification of carbodiimide skeleton of the cyclic carbodiimide compound identified synthesis by IR carbodiimide skeleton of the cyclic carbodiimide uses Nicolet Co. Magna-750, characteristic 2100～2200Cm ^-1 in FT-IR Accordingly carbodiimide This was done by confirming the absorption peak of.
In the examples of the present invention, the following materials were used.

[C-1 component: production of cyclic carbodiimide (CC1)]
[Production Example 2]
Reaction in which 200 ml of o-nitrophenol (0.11 mol), 1,2-dibromoethane (0.05 mol), potassium carbonate (0.33 mol), and N, N-dimethylformamide (DMF) were installed with a stirrer and a heating device The apparatus was charged in an N ₂ atmosphere and reacted at 130 ° C. for 12 hours. After that, 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 A (nitro form).

  Next, intermediate product A (0.1 mol), 5% palladium carbon (Pd / C) (1 g), and 200 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction is performed in a state where hydrogen is constantly supplied at 25 ° C., and the reaction is terminated when there is no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product B (amine body) was obtained.

Next, in a reactor equipped with a stirrer, a heating device, and a dropping funnel, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane are charged and stirred in an N ₂ atmosphere. A solution prepared by dissolving intermediate product B (0.05 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane is 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 C (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 was charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product C (0.05 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, CC1 was obtained by refine | purifying the solid substance obtained by removing dichloromethane. As a result of confirming the structure of CC1 by NMR and IR, it was a structure represented by the following formula.

  As other raw materials, the following were used.

<B component>
B-1: Kuraray Co., Ltd. SEPTON 8006 [Polystyrene-poly (ethylene / butylene) block-polystyrene / glass transition temperature-55 ° C.]
B-2: Hytrel 4057 manufactured by Toray DuPont Co., Ltd. [Polybutylene terephthalate-polytetramethylene glycol block copolymer / glass transition temperature-30 ° C.]
B-3: TPAE-32 manufactured by T & K TOKA Co., Ltd. [Polyetheresteramide elastomer / glass transition temperature-40 ° C.]
B-4: Bondfast 7M [ethylene-glycidyl methacrylate-methyl acrylate copolymer / glass transition temperature-33 ° C.] manufactured by Sumitomo Chemical Co., Ltd.

<B 'component>
B′-1: Hytrel 5557 manufactured by Toray DuPont Co., Ltd. [Polybutylene terephthalate-polytetramethylene glycol block copolymer / glass transition temperature-20 ° C.]
B′-2: G1641HU manufactured by Kraton Polymer Japan Co., Ltd. [polystyrene-poly (ethylene / butylene) block-polystyrene / glass transition temperature−25 ° C.]

<D component>
D-1: Irganox 1076 [n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] manufactured by Ciba Specialty Chemicals Co., Ltd.
D-2: Pade-24G manufactured by ADEKA Corporation [Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite]
D-3: Sandstub P-EPQ [tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite] manufactured by Clariant Japan Co., Ltd.
D-4: Adeka Corporation Adeka Stub AO-412S [3-laurylthiopropionate]

3. Production and Evaluation of Polylactic Acid Resin Pellets Resin composition pellets of polylactic acid resin (component A) and additives were produced by the methods shown in the following examples and comparative examples. Moreover, each value in an Example was calculated | required with the following method.
(1) Deflection temperature under load Using an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-150EN), the cylinder temperature is 230 ° C., the mold temperature is 120 ° C., and the molding cycle is 70 seconds. A test piece conforming to the ISO standard of 10 mm × 4 mm was molded and allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then measured at a load of 0.45 MPa according to ISO 75-1 and 2. did.
(2) Stress ratio of tensile test The resin composition was injected at a cylinder temperature of 230 ° C, a mold temperature of 120 ° C, and a molding cycle of 70 seconds using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN). 1A-shaped molded piece described in ISO527-2 was molded and allowed to stand for 24 hours in an environment at a temperature of 23 ° C. and a relative humidity of 50%, and then a tensile test was performed in accordance with ISO527-1 and ISO527-2. The stress at the upper yield point (yield stress) and the stress at the break point (breaking stress) were measured, and the stress ratio [stress ratio = (breaking stress / yield stress) × 100] was calculated.
(3) Bleed-out test The resin composition was molded using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), 150 mm x 150 mm, 2 mm thick, mold surface polishing # 8000 mold, cylinder temperature 230 Molded pieces were prepared at ℃, mold temperature of 120 ℃, and molding cycle of 70 seconds. Next, letters were written on this molded piece using an oil-based felt pen “Mackey (registered trademark)” manufactured by Zebra Co., Ltd., and then treated for 24 hours under conditions of 60 ° C. × 85% RH. A wipe test was performed. The case where the character could not be wiped off was judged as ○, and the case where the character was wiped off was judged as ×.
(4) Hydrolysis resistance Using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), the resin composition was subjected to ISO 527 at a cylinder temperature of 230 ° C, a mold temperature of 120 ° C, and a molding cycle of 70 seconds. A molded piece of 1A type described in -2. Next, this molded piece was subjected to a wet heat treatment at 80 ° C. × 95% RH for 200 hours. In accordance with ISO527-1 and ISO527-2, a tensile test was performed, and the retention rate [(maximum tensile stress after wet heat treatment / before wet heat treatment) was determined from the maximum tensile stress before wet heat treatment and the maximum tensile stress after wet heat treatment. Maximum tensile stress) × 100] was calculated.

<Example 1>
Using the polylactic acid resin A-1 component produced in Production Example 1-1 as the polylactic acid resin, the composition shown in Table 2 was uniformly premixed by dry blending, and then this premixed mixture was supplied from the first supply port. , Melt extruded and pelletized. Here, the first supply port is a base supply port. The melt extrusion was carried out using a vent type twin screw extruder (TEX30XSST manufactured by Nippon Steel Works) with a diameter of 30 mmφ. The extrusion temperature was C1 / C2 to C11 / D = 10 ° C./230° C./240° C., the screw rotation speed was 150 rpm, the discharge rate was 20 kg / h, and the vent pressure reduction was 3 kPa.
The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours, molded with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), and evaluated. The results are shown in Table 2.

<Example 2>
Except having used the polylactic acid resin A-2 component manufactured by manufacture example 1-2 as a polylactic acid resin, it pelletized by the method similar to Example 1, and implemented the evaluation. The results are shown in Table 2.

<Examples 3 and 5-20, Comparative Examples 1 and 3-6>
Except having used the polylactic acid resin A-3 component manufactured by manufacture example 1-3 as a polylactic acid resin, it pelletized by the method similar to Example 1, and implemented the evaluation. The results are shown in Tables 2-4.

<Example 4>
Except having used the polylactic acid resin A-4 component manufactured by manufacture example 1-4 as a polylactic acid resin, it pelletized by the method similar to Example 1, and implemented the evaluation. The results are shown in Table 2.

<Comparative example 2>
Except having used the polylactic acid resin A'-1 component manufactured by manufacture example 1-5 as a polylactic acid resin, it pelletized by the method similar to Example 1, and the evaluation was implemented. The results are shown in Table 3.

<Examples 1 to 13>
Examples 1 to 13 using a polylactic acid resin having a weight average molecular weight of 100,000 or more and an elastomer having a glass transition temperature of −30 ° C. or less have a stress ratio of 90% or more, no bleed-out, and a frame for glasses. It was suitable as a member.

<Comparative Example 1>
When only the polylactic acid resin was used, the test piece broke before reaching the yield point during the tensile test.

<Comparative example 2>
When a polylactic acid resin having a weight average molecular weight of less than 100,000 was used, the test piece broke before reaching the yield point during the tensile test.

<Comparative Example 3>
Since the amount of elastomer having a glass transition temperature of −30 ° C. or lower was too small, the stress ratio was less than 90%.

<Comparative Example 4>
Since the amount of the elastomer having a glass transition temperature of −30 ° C. or lower was too large, the deflection temperature under load was greatly reduced, and the heat resistance was insufficient for use as a frame member for glasses.

<Comparative Examples 5 and 6>
When an elastomer having a glass transition temperature higher than −30 ° C. was used, the stress ratio was less than 90%.

<Examples 14 to 20>
Furthermore, by combining a carbodiimide compound, it was possible to impart high hydrolysis resistance while maintaining the characteristics suitable as a frame member for spectacles. Moreover, when a carbodiimide compound and an antioxidant were combined, it was possible to impart even higher hydrolysis resistance.

4). Evaluation as a frame member for eyeglasses Using the materials of Examples 3, 5, and 12 and Comparative Examples 1, 2, 3, and 5, an integrally molded product (1) of the nose pad (1a) and the front frame (1b) shown in FIG. ), Ude (2a), and Ear Modern (2b) integrally molded product (2) were prepared and evaluated. The member was prepared by the following method.
That is, using a vertical injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd .: NC-9000), molding was performed at a cylinder temperature of 230 ° C., a mold temperature of 120 ° C., and a molding cycle of 60 seconds, and an integrally molded product (1) And (2) were obtained. The obtained integrally molded product (2) is immersed in a 70 ° C. hot water tank and deformed by hand in consideration of the shape of the user's ear in the hot water tank, and this shape is maintained for 15 seconds at room temperature. The deformed shape was fixed by natural cooling. A frame member for eyeglasses was prepared using the obtained integrally molded product (1) and the integrally molded product (2) deformed in the hot water tank.
The prepared frame member for glasses was used to adjust the shape by bending the ear modern (2b) portion of the integrally molded product (2) by hand at room temperature so as to fit the face of the user. The determination at this time was performed based on the following criteria. The evaluation results are shown in Table 5.
X: The molded product was too hard to be bent by hand.
Δ: Although it could be adjusted by bending by hand, whitening was observed visually.
○: It was possible to adjust by bending by hand, and slight whitening was visually observed.
(Double-circle): It was possible to bend and adjust by hand and there was no whitening visually.

<Example 21>
The frame member for eyeglasses prepared by using the polylactic acid resin having a weight average molecular weight of 100,000 or more and the resin composition having a glass transition temperature of −30 ° C. or less used in Example 3 is bent and adjusted by hand. And no whitening was observed, and it was very suitable as a spectacle frame member.

<Example 22>
The frame member for eyeglasses prepared using the polylactic acid resin having a weight average molecular weight of 100,000 or more and the resin composition having a glass transition temperature of −30 ° C. or less used in Example 5 is bent and adjusted by hand. It was possible to check the whitening and it was suitable as a spectacle frame member.

<Example 23>
Created by using a polylactic acid resin having a weight average molecular weight of 100,000 or more used in Example 12, and a resin composition comprising an elastomer containing an epoxy group having a glass transition temperature of −30 ° C. or less and an elastomer containing no epoxy group. The spectacle frame member can be bent and adjusted by hand, and whitening is not observed at all, which is very suitable as a spectacle frame member.

<Comparative Example 7>
The frame member for eyeglasses produced using the resin composition consisting only of the polylactic acid resin used in Comparative Example 1 was too hard to bend by hand because the molded product was too hard.

<Comparative Example 8>
The frame member for eyeglasses prepared by using a polylactic acid resin having a weight average molecular weight of less than 100,000 and a resin composition having a glass transition temperature of −30 ° C. or less used in Comparative Example 2 is bent and adjusted by hand. Although it was possible, the cracked severe whitening was observed in the molded product.

<Comparative Example 9>
Glasses made of a polylactic acid resin having a weight average molecular weight of 100,000 or more used in Comparative Example 3 and an elastomer having a glass transition temperature of −30 ° C. or less, and the addition amount of the elastomer being smaller than a specified range. Although it was possible to bend and adjust the frame member by hand, whitening was observed in the molded product.

<Comparative Example 10>
The frame member for eyeglasses prepared by using a polylactic acid resin having a weight average molecular weight of 100,000 or more and a resin composition made of an elastomer having a glass transition temperature higher than −30 ° C. used in Comparative Example 5 is bent and adjusted by hand. Although it was possible, whitening was seen in the molded product.

1 Nose pad and forehead integrated molding 1a Nose pad 1b Forehead 2 Ude and ear modern integrated molding 2a Ude 2b Ear modern

Claims (7)

A resin composition comprising 20 to 90 parts by weight of (B) an elastomer (B component) having a glass transition temperature of −30 ° C. or less with respect to 100 parts by weight of a polylactic acid resin (A component) having a weight average molecular weight of 100,000 or more. Ri more vegetables,
In the tensile test based on ISO527-1 and ISO527-2, the resin composition has an upper yield point, and the ratio of the stress at the upper yield point and the stress at the fracture point represented by the following formula (2) is A frame member for spectacles that is 90% or more .
Stress ratio = (breaking stress / yield stress) × 100 (2)   A poly-L lactic acid resin (A-1 component) containing 90 mol% or more of L-lactic acid units and an A-component containing 90 mol% or more of D-lactic acid units (A-2 component) The spectacle frame member according to claim 1, wherein the spectacle frame member is contained and the weight ratio of the A-1 component and the A-2 component is in the range of 10:90 to 90:10. The component A has a stereocomplex crystallinity represented by the following formula (1) using a melting enthalpy in a temperature rising process of differential scanning calorimetry (DSC) measurement, and the degree of stereocomplexity is 80% or more. Eyeglass frame member.
Stereo complex crystallinity = [ΔHms / (ΔHms + ΔHmh)] × 100 (1)
[In the formula (1), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal, which appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]   The frame member for spectacles according to any one of claims 1 to 3, comprising 0.01 to 10 parts by weight of a carbodiimide compound (C component) with respect to 100 parts by weight of the A component.   0.01 to 2 parts by weight of at least one antioxidant (D component) selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds with respect to 100 parts by weight of component A The frame member for spectacles of any one of Claims 1-4 containing these. The frame member for spectacles according to any one of claims 1 to 5 , which is created by bending a molded product formed by injection molding, extrusion molding, thermoforming, blow molding or foam molding. The frame member for glasses according to claim 6 , wherein the frame member for glasses is Ude or ear modern.

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