JP5018697B2 - Molded body and method for producing the same - Google Patents

Description

  The present invention relates to a molded article comprising a polylactic acid resin and a polyacetal resin, excellent in transparency and heat resistance, and sufficiently crystallized, and a method for producing the same.

  Polylactic acid resin is biodegradable, has a high melting point, can be melt-molded, and can be obtained as a transparent amorphous molded product immediately after molding. Has been. However, in the state of a transparent molded body, since it is amorphous, there is a large practical problem that it is inferior in heat resistance.

  In order to improve this heat resistance, the spherulite size becomes visible light by increasing the crystallinity by holding the mold temperature close to the crystallization temperature during molding or heat-treating the transparent molded body obtained after molding. Since the wavelength becomes longer than the wavelength of and becomes opaque, it is a very difficult problem to achieve both transparency and heat resistance.

  With respect to this problem, Patent Documents 1 and 2 disclose a method in which a compound having a melting point in a specific temperature range is mixed with an aliphatic polyester, particularly a polylactic acid resin, and crystallized at the time of molding or immediately after molding. Has been. However, in this method, although the transparency is improved, the heat resistance is not yet fully satisfied.

  On the other hand, a technique of blending and using two or more polymers is widely known as a polymer alloy, and this polymer alloy is widely used for the purpose of improving the defects of individual polymers. However, when two or more kinds of polymers are mixed, in many cases, the dispersibility between the polymers is poor, and the polymer cannot be processed into the shape of a pellet or a molded product, or tends to exhibit inferior characteristics.

  However, in rare cases, two types of polymers may form a uniform amorphous phase, and this type of polymer is generally expected to exhibit excellent properties such as transparency as a compatible or miscible polymer alloy. There are few examples.

  Polyethylene glycol (for example, Non-Patent Document 1) and polymethyl methacrylate (for example, Non-Patent Document 2) are known as polymers compatible with the polylactic acid resin. When these polymers are mixed, Has a problem that the heat resistance of the polylactic acid resin is greatly reduced.

  Polyvinylphenol (for example, Non-Patent Document 3) is known as a polymer that is compatible with the polyacetal resin, but since polyvinylphenol generally has a low molecular weight, in this case, the resin physical properties after mixing are low. There was a problem of lowering.

On the other hand, Patent Document 3 discloses that a polylactic acid resin and a polyacetal resin are compatible. However, a transparent and crystallized molded body has not been obtained even by using the method described in the document.
JP-A-9-278991 (paragraphs [0018]-[0045]) JP 11-5849 A (paragraphs [0013]-[0023]) International Publication No. 03/014224 Pamphlet Polymer 37 (26), 5849-5857 (1996). Polymer 39 (26), pages 6891-6897 (1998) Polymer 33 (4), pages 760-766 (1992)

  The object of the present invention has been achieved as a result of studying the solution of the above-described problems in the prior art, and the object of the present invention is a molded article that is excellent in transparency and heat resistance and is sufficiently crystallized. It is in providing a body and its manufacturing method.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition formed by blending a polylactic acid resin and a polyacetal resin exhibits excellent characteristics that meet the above-mentioned purpose, The present invention has been reached.

That is, the present invention
(1) Among the total lactic acid components, the L-form is contained in a resin composition comprising 80% or more of the L-form or a polylactic acid resin containing 80% or more of the D-form, a polyacetal resin, and an amide compound. A molded body in which the proportion of crystallization of the molded body represented by the formula (1) is 60% or more, and the polylactic acid resin and the polyacetal resin are compatible in the molded body,
[(ΔHm−ΔHc) / ΔHm] × 100 (1)
[In the formula, ΔHm represents the crystal melting enthalpy of the molded body, and ΔHc represents the crystallization enthalpy at elevated temperature of the molded body. ]
(2) The molded product according to the above (1), which is 99 to 60 parts by weight of the polylactic acid resin when the total of the polylactic acid resin and the polyacetal resin is 100 parts by weight,
(3) The molded product according to (1) or (2), wherein the amount of the amide compound is 0.1 to 10 parts by weight when the total of the polylactic acid resin and the polyacetal resin is 100 parts by weight. ,
(4) The molded product according to any one of the above (1) to (3), wherein the amide compound is at least one selected from alicyclic amides and aromatic amides,
(5) The amide compound is selected from N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane, trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, and terephthalic acid dianilide. The molded product according to any one of (1) to (4), which is at least one kind
(6) The molded product according to any one of the above (1) to (5), having a portion having a thickness of 20 μm or more and a haze value of 30% or less,
(7) The molded product according to any one of the above (1) to (5) having a portion having a thickness of 1 mm or more and a haze value of 20% or less, and (8) a polylactic acid resin, The molded product according to any one of the above (1) to (7), which is a polylactic acid resin containing 98% or more of L-form or 98% or more of D-form .

  As described above, the molded article of the present invention is an excellent crystallized molded article excellent in transparency and heat resistance. By utilizing these excellent characteristics, electrical / electronic parts, building members, and automobile parts are used. It can be used for various applications such as various packaging materials and daily necessities.

  Hereinafter, the present invention will be described in detail.

  The polylactic acid resin used in the present invention is a polymer having L-lactic acid and / or D-lactic acid as a main constituent, but other copolymer components other than lactic acid may be used as long as the object of the present invention is not impaired. You may include as other monomer units. Specific examples of other monomer units mentioned here include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, Glycerin, pentaerythritol, bisphenol A, glycol compounds such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid , Terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-dipheny Ether dicarboxylic acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid and 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and hydroxybenzoic acid, Examples include lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. These copolymer components can be used alone or in combination of two or more. Moreover, as content of these copolymerization components, it is preferable to set it as content of 30 mol% or less normally in all the monomer components, and it is more preferable that it is 10 mol% or less.

  In the present invention, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component from the viewpoint of compatibility. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90% or more. More preferably, the L-form is contained at 95% or more, or the D-form is contained at 95% or more, and the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Particularly preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

The melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. The melting point of the polylactic acid resin is usually increased by increasing the optical purity of the lactic acid component, and the polylactic acid resin having a melting point of 120 ° C. or higher contains 90% or more of the L form or 90% or more of the D form. In addition, the polylactic acid resin having a melting point of 150 ° C. or higher contains 95% or more of L form or 95% of D form.
By being contained above, it can be obtained.

  The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be substantially molded, but from the viewpoint of obtaining a molded article having excellent mechanical properties, the weight average molecular weight is Usually, it is 10,000 or more, preferably 40,000 or more, and more preferably 80,000 or more. The weight average molecular weight here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  As a method for producing the polylactic acid resin, a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.

  The polyacetal resin used in the present invention is a polymer having an oxymethylene unit as a main repeating unit, and is mainly composed of a so-called polyacetal homopolymer obtained by a polymerization reaction using formaldehyde or trioxane as a main raw material, or mainly composed of an oxymethylene unit. It may be any so-called polyacetal copolymer containing 15% by weight or less of oxyalkylene units having 2 to 8 adjacent carbon atoms in the chain, and also a copolymer containing other structural units, ie a block copolymer, Either a terpolymer or a crosslinked polymer may be used, and these may be used alone or in combination of two or more. From the viewpoint of thermal stability, a polyacetal copolymer is preferable.

  There is no restriction | limiting in particular about the manufacturing method of the polyacetal resin in this invention, It can manufacture by a well-known method. As an example of a typical method for producing a polyacetal homopolymer, high-purity formaldehyde is introduced into an organic solvent containing a basic polymerization catalyst such as an organic amine, an organic or inorganic tin compound, or a metal hydroxide. Examples of the method include polymerizing and filtering the polymer, followed by heating in acetic anhydride in the presence of sodium acetate to acetylate the polymer terminal.

  As a typical method for producing a polyacetal copolymer, a high purity trioxane and a copolymer component such as ethylene oxide and 1,3-dioxolane are introduced into an organic solvent such as cyclohexane, and boron trifluoride diethyl ether complex is prepared. After the cationic polymerization using a Lewis acid catalyst such as the above, the production method by deactivating the catalyst and stabilizing the end group, or into the self-cleaning stirrer without using any solvent, trioxane Examples thereof include a method in which a copolymer component and a catalyst are introduced and bulk polymerization is performed, and then an unstable terminal is further decomposed and removed.

  The viscosity of these polyacetal resins is not particularly limited as long as it can be used as a molding material, but melt index (MI) can be measured by ASTM D1238 method, and MI is 1.0 to 50 g / 10 min. It is preferable that it is a thing of the range, and it is especially preferable that it is a thing of 1.5-35 g / 10min.

  Further, as the polyacetal resin, it is preferable to use a resin containing a heat stabilizer or a generated gas scavenger in advance, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), calcium ricinolate, Cyanoguanazine, hexamethylene bis (3,5-t-butyl-4-hydroxyhydrocyanate), melamine-formaldehyde resin, nylon 6/66, nylon 66/610/6, nylon 612/6, tetrakis [methylene (3 5-di-t-butyl-4-hydroxyhydrocyanate)] methane, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol [3- (3,5-di-tert-butyl-5-methyl-4-hydroxyphen It is preferred that at least one Le) propionate] are contained ( "/" indicates copolymerization).

  In the present invention, the composition of the polylactic acid resin and the polyacetal resin is transparent and facilitates the production of a molded product having a crystallization ratio within the range of the present invention, and further imparts excellent heat resistance. Therefore, the polylactic acid resin is preferably 99 to 50 parts by weight, more preferably 99 to 60 parts by weight, and more preferably 99 to 70 parts by weight with respect to 100 parts by weight of the total of the polylactic acid resin and the polyacetal resin. More preferably, the amount is 99 to 80 parts by weight. If the polylactic acid resin exceeds 99 parts by weight, the heat resistance is insufficient, and if it is less than 50 parts by weight, the transparency may be impaired. In addition, this blending composition may be biodegradable taking advantage of the properties of polylactic acid resin.

  In the present invention, the polylactic acid resin and the polyacetal resin are usually compatible in the molded article. Therefore, transparency can be achieved even though a highly crystalline polyacetal resin is used. “Compatibilization” as used herein is used to describe the formation of a polymer mixture that forms a homogeneous phase in the amorphous phase at the molecular level. That is, when one or both of the formulations forms both a crystalline phase and an amorphous phase, compatible means that the amorphous phase is mixed at the molecular level.

  The determination of compatibility in a formulation can be made in several ways. The most common method for judging the compatibility is a method for judging by the glass transition temperature. In compatible formulations, the glass transition temperature varies from that of each individual and often exhibits a single glass transition temperature. As a method for measuring the glass transition temperature, any of a method of measuring with a differential scanning calorimeter (DSC) and a method of measuring with a dynamic viscoelasticity test can be used.

  However, since the polyacetal resin is highly crystalline, there is a problem that the glass transition temperature becomes unclear when the content of the polyacetal resin is large. In this case, the crystallization temperature of the polyacetal resin can be used as the compatibility determination. That is, when the polyacetal resin forms a compatible compound with a resin having a slower crystallization rate than the polyacetal resin itself, the crystallization rate of the polyacetal resin is lower than that of a single substance. Therefore, the decrease in the crystallization rate can be determined by the crystallization temperature at the time of temperature decrease measured by DSC.

  In the present invention, an amide compound is blended from the viewpoint of further improving transparency and heat resistance.

  The amide compound used in the present invention is not particularly limited as long as it is a compound usually having a bond called an amide bond, and any of aliphatic amide, alicyclic amide, aromatic amide and the like can be used. However, from the viewpoint of improving transparency and heat resistance, alicyclic amides and aromatic amides are more preferable.

  The aliphatic amide is not particularly limited as long as it is an amide compound composed of a chain molecule that does not contain any ring structure such as an alicyclic ring or an aromatic ring in the molecule.

  Specific examples thereof include acetic acid amide, propionic acid amide, lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, hydroxystearic acid amide and N-oleyl palmitic acid. Acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl oleic acid amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide, methylol stearic acid amide, methylol behenic acid amide, Methylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis capric acid amide, ethylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis erucic acid amide, ethylene bis behenic acid amide Ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, butylene bisstearic acid amide, hexamethylene bis oleic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis Hydroxystearic acid amide, oxalic acid amide, malonic acid amide, succinic acid amide, glutaric acid amide, adipic acid amide, pimelic acid amide, suberic acid amide, azelaic acid amide, sebacic acid amide, 1,12-dodecanedioic acid amide, 1,14-tetradecanedioic acid amide, 1,18-octadecanedioic acid amide, citric acid amide, methanetricarboxylic acid amide, tricarballylic acid amide, propenetricarboxylic acid amide, pentanetricarboxylic acid amide, etante Lacarboxylic acid amide, propanetetracarboxylic acid amide, pentanetetracarboxylic acid amide, 1,2,3,4-butanetetracarboxylic acid amide, dodecanetetracarboxylic acid amide, pentanepentacarboxylic acid amide, tetradecanehexacarboxylic acid amide, ethylenediamine tetra Acetic acid amide, nitrilotriacetic acid amide, ethylene glycol bis (β-aminoethyl ether) N, N, N ′, N′-tetraacetic acid amide, diethylenetriaminepentaacetic acid amide, N-hydroxyethylethylenediamine-N, N ′, N ′ Triacetamide, 1,3-diaminopropan-2-ol-, N, N ′, N′-tetraacetamide, 1,2-diaminopropane-N, N, N ′, N′-tetraacetamide, Triethylenetetramine hexaacetamide, nitrilotripropionamide, 1 6-hexanediaminetetraacetic acid amide, N- (2-carboxyethyl) iminodiacetic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N-distearyl adipine Acid amide, N, N′-distearyl sebacic acid amide, N, N′-diacetylethylenediamine, N, N′-diethylethylenediamine, N, N′-dibutylethylenediamine, N, N′-diacetyl-1,6-hexane Diamine, N, N′-diethylcarbonyl-1,6-hexanediamine, N, N′-dibutylcarbonyl-1,6-hexanediamine, N, N, N ′, N′-tetramethylcarbonyl-1,6- Hexanediamine, N-butyl-N′-stearyl urea, N-propyl-N′-stearyl urea, N, N′-bisste Examples include rilurea, hexamethylenebisstearylurea, and palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, hydroxystearic acid amide, from the viewpoint of improving transparency and heat resistance. N-oleyl palmitic acid amide, N-stearyl erucic acid amide, ethylene biscapric acid amide, ethylene bis oleic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, N, N′-diacetylethylenediamine, N, N ′ -Diacetyl-1,6-hexanediamine is preferable, and ethylene bislauric acid amide and ethylene bis stearic acid amide are more preferable.

  The alicyclic amide is not particularly limited as long as it is an amide compound that contains an alicyclic structure in the molecule and does not contain an aromatic ring.

  Specific examples thereof include cyclopropanecarboxylic acid amide, cyclobutanecarboxylic acid amide, cyclopentanecarboxylic acid amide, cyclopentenecarboxylic acid amide, cyclohexanecarboxylic acid amide, cyclohexenecarboxylic acid amide, cycloheptanecarboxylic acid amide, methylcyclopentanecarboxylic acid amide. , Butylcyclohexenecarboxylic acid amide, methylcycloheptanecarboxylic acid amide, methylcyclohexanecarboxylic acid amide, ethylcyclohexanecarboxylic acid amide, propylcyclohexanecarboxylic acid amide, butylcyclohexanecarboxylic acid amide, pentylcyclohexanecarboxylic acid amide, hexylcyclohexanecarboxylic acid amide, Phenylcyclohexanecarboxylic acid amide, chlorocyclohexanecarboxylic acid amide Bromocyclohexanecarboxylic acid amide, dimethylcyclohexanecarboxylic acid amide, di-t-butylcyclohexanecarboxylic acid amide, methoxycyclohexanecarboxylic acid amide, ethoxycyclohexanecarboxylic acid amide, dimethoxycyclohexanecarboxylic acid amide, diethoxycyclohexanecarboxylic acid amide, dichlorocyclohexanecarboxylic acid amide Acid amide, trimethylcyclohexanecarboxylic acid amide, trimethoxycyclohexanecarboxylic acid amide, triethoxycyclohexanecarboxylic acid amide, cyclohexylacetic acid amide, methylcyclohexylacetic acid amide, methoxycyclohexylacetic acid amide, cyclohexylpropionic acid amide, cyclohexylbutyric acid amide, N-oleylcyclohexane Carboxylic acid amide, N-steer Cyclohexanecarboxylic acid amide, methylolcyclohexanecarboxylic acid amide, methylenebiscyclohexanecarboxylic acid amide, ethylenebiscyclohexanecarboxylic acid amide, hexamethylenebiscyclohexanecarboxylic acid amide, 1,2-cyclohexanedicarboxylic acid amide, 1,4-cyclohexanedicarboxylic acid Amides, 1,4-cyclohexanediacetamide, cyclohexanetricarboxylic acid amide, cyclobutanetetracarboxylic acid amide, cyclopentanetetracarboxylic acid amide, cyclohexanetetracarboxylic acid amide, 5- (succinic acid amide) -3-methyl-3-cyclohexene -1,2-dicarboxylic acid amide, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid amide, cyclohexanehexa Carboxylic acid amide, 1,2-cyclohexanediaminetetraacetic acid amide, 2,3,5-tricarboxycyclopentylacetic acid amide, 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid amide, 3,5,6- Tricarboxynorbornene-2-acetic acid amide, thiobis (norbornene-2,3-dicarboxylic acid amide), bicyclo [4.2.0] octane-3,4,7,8-tetracarboxylic acid amide, 1,1 '-Bicyclopropane-2,2', 3,3'-tetracarboxylic amide, pyrazine-2,3,5,6-tetracarboxylic amide, 2,3,4,5,6,7,12,13 -Octahydrophenanthrene-3,4,5,6-tetracarboxylic amide, N, N'-dioleyl-1,2-cyclohexanedicarboxylic amide, N, N'-diole -1,4-cyclohexanedicarboxylic acid amide, N, N-distearyl-1,2-cyclohexanedicarboxylic acid amide, N, N′-distearyl-1,4-cyclohexanedicarboxylic acid amide, acetic acid cyclohexylamide, propionic acid Cyclohexylamide, lauric acid cyclohexylamide, palmitic acid cyclohexylamide, oleic acid cyclohexylamide, stearic acid cyclohexylamide, erucic acid cyclohexylamide, behenic acid cyclohexylamide, ricinoleic acid cyclohexylamide, hydroxystearic acid cyclohexane Hexylamide, oxalic acid dicyclohexylamide, malonic acid dicyclohexylamide, succinic acid dicyclohexylamide, glutaric acid dicyclohexylamide, adipic acid dicyclohexylamide Pimelic acid dicyclohexylamide, suberic acid dicyclohexylamide, azelaic acid dicyclohexylamide, sebacic acid dicyclohexylamide, 1,12-dodecanedioic acid dicyclohexylamide, 1,14-tetradecanedioic acid dicyclohexylamide, 1, 18-octadecanedioic acid dicyclohexylamide, citric acid tricyclohexylamide, methanetricarboxylic acid tricyclohexylamide, tricarballylic acid tricyclohexylamide, propenetricarboxylic acid tricyclohexylamide, pentanetricarboxylic acid tricyclohexylamide, ethanetetracarboxylic acid tetracyclohexylamide Propanetetracarboxylic acid tetracyclohexylamide, pentanetetracarboxylic acid tetracyclohexylamide, 1,2 , 3,4-Butanetetracarboxylic acid tetracyclohexylamide, dodecanetetracarboxylic acid tetracyclohexylamide, pentanepentacarboxylic acid pentacyclohexylamide, tetradecanhexacarboxylic acid hexacyclohexylamide, ethylenediaminetetraacetic acid tetracyclohexylamide, nitrilotriacetic acid tricyclohexylamide , Ethylene glycol bis (β-aminoethyl ether) N, N, N ′, N′-tetraacetic acid tetracyclohexylamide, diethylenetriaminepentaacetic acid pentacyclohexylamide, N-hydroxyethylethylenediamine-N, N ′, N′-triacetic acid Tricyclohexylamide, 1,3-diaminopropan-2-ol-N, N, N ′, N′-tetraacetic acid tetracyclohexylamide, 1,2-diaminopro -N, N, N ', N'-tetraacetic acid tetracyclohexylamide, triethylenetetraminehexaacetic acid hexacyclohexylamide, nitrilotripropionic acid tricyclohexylamide, 1,6-hexanediaminetetraacetic acid tetracyclohexylamide, N- ( 2-carboxyethyl) iminodiacetic acid dicyclohexylamide, 1,2-cyclohexanecarboxylic acid cyclohexylamide, 1,4-cyclohexanecarboxylic acid cyclohexylamide, 1,2-cyclohexanedicarboxylic acid dicyclohexylamide, 1,4-cyclohexane Dicarboxylic acid dicyclohexylamide, 1,4-cyclohexanediacetic acid dicyclohexylamide, cyclohexanetricarboxylic acid tricyclohexylamide, cyclohexanetetracarboxylic acid tetracyclohexylamide Amide, cyclohexanehexacarboxylic acid hexacyclohexylamide, 1,2-cyclohexanediaminetetraacetic acid tetracyclohexylamide, N, N′-diacetyl-1,4-diaminocyclohexane, N, N′-dicyclohexanecarbonyl-1,6- Hexanediamine, N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane, N, N′-dicyclohexanecarbonyl-1,2-diaminocyclohexane, N, N′-dicyclohexylurea, N- (p- Acetylbenzenesulfonyl) -N′-cyclohexylurea and the like, and from the viewpoint of improving transparency and heat resistance, cyclohexanecarboxylic acid amide, lauric acid cyclohexylamide, stearic acid cyclohexylamide, 1,2,3, 4-butanetetraca Boronic acid tetracyclohexylamide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, and N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane are preferred, and lauric acid cyclohexylamide, 1,2,3,4 -Butanetetracarboxylic acid tetracyclohexylamide and N, N'-dicyclohexanecarbonyl-1,4-diaminocyclohexane are more preferred, and N, N'-dicyclohexanecarbonyl-1,4-diaminocyclohexane is most preferred.

  The aromatic amide is not particularly limited as long as it is an amide compound containing an aromatic ring or an aromatic polycyclic structure in which aromatic rings are condensed in the molecule.

  Specific examples thereof include benzoic acid amide, 1-naphthoic acid amide, 2-naphthoic acid amide, methyl benzoic acid amide, ethyl benzoic acid amide, propyl benzoic acid amide, butyl benzoic acid amide, pt-butyl benzoic acid amide. , Pentyl benzoic acid amide, hexyl benzoic acid amide, phenyl benzoic acid amide, cyclohexyl benzoic acid amide, chlorobenzoic acid amide, bromobenzoic acid amide, methoxybenzoic acid amide, ethoxybenzoic acid amide, dimethyl benzoic acid amide, di-t- Butylbenzoic acid amide, dimethoxybenzoic acid amide, diethoxybenzoic acid amide, dichlorobenzoic acid amide, trimethylbenzoic acid amide, trimethoxybenzoic acid amide, triethoxybenzoic acid amide, phenylacetic acid amide, methylphenylacetic acid amide, methoxypheny Acetic acid amide, phenylpropionic acid amide, phenylbutyric acid amide, N-oleyl benzoic acid amide, N-stearyl benzoic acid amide, N-cyclohexyl benzoic acid amide, methylene bis benzoic acid amide, ethylene bis benzoic acid amide, hexamethylene bis benzoic acid Acid amide, m-xylylene bis stearic acid amide, o-xylylene bis stearic acid amide, p-xylylene bis stearic acid amide, m-xylylene bis-12-hydroxystearic acid amide, m-xylylene biscyclohexanecarboxylic acid amide , M-xylylenedibenzoic acid amide, o-xylylenedibenzoic acid amide, p-phenylenediacetic acid amide, p-phenylenediethanic acid amide, phthalic acid amide, 4-t-butylphthalic acid amide, isophthalic acid amide, 5-t- Spotted Isophthalic acid amide, terephthalic acid amide, 1,8-naphthalic acid amide, 1,4-naphthalenedicarboxylic acid amide, 2,6-naphthalenedicarboxylic acid amide, 2,7-naphthalenedicarboxylic acid amide, diphenic acid amide, 3,3 '-Biphenyl dicarboxylic acid amide, 4,4'-biphenyl dicarboxylic acid amide, 4,4'-binaphthyl dicarboxylic acid amide, dithiosalicylic acid amide, trimesic acid amide, trimellitic acid amide, phenylcyclopentanecarboxylic acid amide, benzenetetracarboxylic acid Amides, benzophenone tetracarboxylic acid amides, biphenyl tetracarboxylic acid amides, biphenyl ether tetracarboxylic acid amides, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid amides, diphenylmethane tetracarboxylic acid amides Amide, perylenetetracarboxylic amide, naphthalenetetracarboxylic amide, 4,4′-dinaphthalic amide, benzidine-3,3′-dicarboxyl-N, N′-tetraacetic amide, diphenylpropanetetracarboxylic amide, anthracene Tetracarboxylic amide, phthalocyanine tetracarboxylic amide, benzenehexacarboxylic amide, isophthalic dioleyl amide, terephthalic dioleyl amide, isophthalic acid distearyl amide, terephthalic acid distearyl amide, terephthalic acid dicyclohexyl amide, 2,6 -Naphthalenedicarboxylic acid distearylamide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, 2,6-naphthalenedicarboxylic acid bis (2-methylcyclohexylamide), trimesic acid tris ( -Butylamide), trimesic acid tris (2-methylcyclohexylamide), trimellitic acid tris (t-butylamide), trimellitic acid tris (2-methylcyclohexylamide), acetic acid anilide, acetic acid benzylamide, acetic acid-4-cyclohexylanilide, Acetic acid-p-toluidine amide, propionic acid anilide, lauric acid anilide, lauric acid benzylamide, lauric acid-4-cyclohexylanilide, lauric acid-p-toluidine amide, palmitic acid anilide, oleic acid anilide, stearic acid anilide, stearin Acid benzylamide, stearic acid-4-cyclohexylanilide, stearic acid-p-toluidineamide, erucic acid anilide, behenic acid anilide, ricinoleic acid anilide, hydroxystearic acid anilide Oxalic acid dianilide, oxalic acid dibenzylamide, oxalic acid bis (4-cyclohexylanilide), oxalic acid bis (p-toluidineamide), malonic acid dianilide, succinic acid dianilide, glutaric acid dianilide, adipic acid dianilide, adipic acid diacid Benzylamide, adipic acid bis (4-cyclohexylanilide), adipic acid bis (p-toluidineamide), pimelic acid dianilide, suberic acid dianilide, azelaic acid dianilide, sebacic acid dianilide, 1,12-dodecanedioic acid dianilide, 1 , 14-tetradecanedioic acid dianilide, 1,18-octadecanedioic acid dianilide, citric acid trianilide, methanetricarboxylic acid trianilide, tricarbaryl acid trianilide, propenetricarboxylic acid trianilide, pentanetricarbo. Acid trianilide, ethanetetracarboxylic acid tetraanilide, 1,2,3,4-butanetetracarboxylic acid tetraanilide, dodecanetetracarboxylic acid tetraanilide, pentanepentacarboxylic acid pentaanilide, tetradecanehexacarboxylic acid hexaanilide, ethylenediaminetetraacetic acid Tetraanilide, 1,4-cyclohexanecarboxylic acid anilide, 1,4-cyclohexanecarboxylic acid-4-cyclohexylanilide, 1,4-cyclohexanecarboxylic acid-p-toluidine amide, 1,4-cyclohexane Carboxylic acid benzylamide, 1,4-cyclohexanedicarboxylic acid dianilide, 1,4-cyclohexanedicarboxylic acid bis (4-cyclohexylanilide), 1,4-cyclohexanedicarboxylic acid dibenzylamide, 1,4 -Cyclohex Dicarboxylic acid bis (p-toluidineamide), benzoic acid anilide, benzoic acid-p-toluidineamide, benzoic acid benzylamide, terephthalic acid dianilide, terephthalic acid dibenzylamide, 2,6-naphthalenedicarboxylic acid dianilide, 2,6 -Naphthalenedicarboxylic acid dibenzylamide, trimesic acid trianilide, trimesic acid tri (4-cyclohexylanilide), trimesic acid tri-p-toluidine amide, trimesic acid tribenzylamide, trimellitic acid tribenzylamide, N, N'-diacetyl -O-phenylenediamine, N, N'-diacetyl-p-phenylenediamine, N, N'-diacetyl-2,3-diaminotoluene, N, N'-diacetyl-1,5-diaminonaphthalene, N, N ' , N ″ -triacetyl-1, , 5-triaminobenzene, N, N′-dicyclohexanecarbonyl-o-phenylenediamine, N, N′-dicyclohexanecarbonyl-p-phenylenediamine, N, N′-dicyclohexanecarbonyl-2,3 -Diaminotoluene, N, N'-dicyclohexanecarbonyl-1,5-diaminonaphthalene, N, N ', N "-tricyclohexanecarbonyl-1,3,5-triaminobenzene, N, N'-dibenzoyl -1,4-diaminobutane, N, N′-dibenzoyl-1,6-diaminohexane, N, N′-dibenzoyl-1,4-diaminocyclohexane, N, N′-dibenzoyl-o-phenylenediamine, N, N′-dibenzoyl-p-phenylenediamine, N, N′-dibenzoyl-2,3-diaminotoluene, N, N ′ -Dibenzoyl-1,5-diaminonaphthalene, N, N ', N "-tribenzoyl-1,3,5-triaminobenzene, xylylene bisstearyl urea, toluylene bisstearyl urea, diphenylmethane bisstearyl urea, diphenylmethane bis Examples thereof include lauryl urea and N-phenyl-N′-stearyl urea. From the viewpoint of improving transparency and heat resistance, ethylene bisbenzoic acid amide, m-xylylene bisstearic acid amide, p-xylylene bisstearic acid Amides, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, trimesic acid tris (t-butylamide), trimesic acid tris (2-methylcyclohexylamide), adipic acid dianilide, adipic acid dibenzylamide, adipic acid bis (4-cyclohexane) Hexylanilide ), Adipic acid bis (p-toluidine amide), 1,4-cyclohexanedicarboxylic acid dianilide, 1,4-cyclohexanedicarboxylic acid bis (p-toluidine amide), terephthalic acid dianilide, terephthalic acid dibenzylamide, 2,6-naphthalenedicarboxylic acid dianilide, trimesic acid trianilide, trimesic acid tri (4-cyclohexylanilide), trimesic acid tri-p-toluidine amide, trimesic acid tribenzylamide, trimellitic acid tribenzylamide, 1,4-cyclohexane Dicarboxylic acid bis (p-toluidine amide), N, N′-dicyclohexanecarbonyl-1,5-diaminonaphthalene, N, N′-dibenzoyl-1,4-diaminobutane, N, N′-dibenzoyl-1, 4-diaminocyclohexane, N, '-Dibenzoyl-p-phenylenediamine and N, N'-dibenzoyl-1,5-diaminonaphthalene are preferable, and further, trimesic acid tris (t-butylamide), 2,6-naphthalenedicarboxylic acid dicyclohexylamide, 1,4- More preferred are cyclohexanedicarboxylic acid dianilide, terephthalic acid dianilide, terephthalic acid dibenzylamide, N, N′-dicyclohexanecarbonyl-1,5-diaminonaphthalene, N, N′-dibenzoyl-1,4-diaminocyclohexane. Trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, and terephthalic acid dianilide are most preferable.

  The compounding amount of the amide compound used in the present invention is not particularly limited, but it is 0 when the total of the polylactic acid resin and the polyacetal resin is 100 parts by weight from the viewpoint of improving transparency and heat resistance. 0.1 to 10 parts by weight is preferable, 0.1 to 8 parts by weight is more preferable, and 0.1 to 5 parts by weight is most preferable. If the amount is less than 0.1 parts by weight, the effect of improving transparency and heat resistance is insufficient, and if it exceeds 10 parts by weight, the transparency may be impaired.

  The method for producing the amide compound used in the present invention is not particularly limited, and aliphatic, alicyclic or aromatic carboxylic acids and derivatives thereof and aliphatic, alicyclic or aromatic amines and derivatives thereof are used. Thus, it can be produced by amidation by a known method.

  In the molded product of the present invention, the term “transparent” means that there is a portion where the character can be read when the molded product is superimposed on a printed matter such as a newspaper. In the present invention, the molded body preferably has a portion having a thickness of 20 μm or more and a portion having a haze value of 30% or less, and has a portion having a haze value of 20% or less. Is more preferable, and a molded body having a portion of 15% or less is further preferable. Among them, it is more preferable that the molded body has a portion satisfying the haze value in a portion where the thickness of the molded body is 100 μm or more, and the thickness of the molded body is preferably 500 μm or more, particularly preferably 1 mm or more. It has a portion that satisfies the haze value. In addition, haze can be measured using a haze meter etc. according to JIS-K7105.

The molded body of the present invention is a molded body that is sufficiently crystallized with a crystallization ratio of the molded body represented by the following formula (1) being 60% or more.
[(ΔHm−ΔHc) / ΔHm] × 100 (1)
[In the formula, ΔHm represents the crystal melting enthalpy of the molded body, and ΔHc represents the crystallization enthalpy at elevated temperature of the molded body. ]

  ΔHm and ΔHc can be determined by thermal measurement using a differential scanning calorimeter (DSC), and 10 mg of a sample cut from the molded body, 0 ° C. to 30 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere. It is measured by raising the temperature from the temperature range to a temperature range of 200 ° C. or higher.

  In the present invention, the ratio of crystallization of the molded product represented by the above formula (1) is preferably higher, but specifically, it is preferably 70% or more, more preferably 80% or more. 90% or more is particularly preferable. If the ratio of crystallization of the molded body represented by the above formula (1) is 60% or more, preferably 80% or more, the heat resistance is remarkably improved.

  ΔHm and ΔHc are not particularly limited as long as the ratio represented by the above formula (1) satisfies the scope of the present invention, but the ratio of crystallization increases as ΔHm is higher and ΔHc is lower. In view of the effect of excellent heat resistance, it is preferable. Specifically, when ΔHm is 20 J / g or more, preferably 40 J / g or more, more preferably 50 J / g or more, more preferably 60 J / g or more, the heat resistance is remarkably improved, and ΔHc is 30 J / g or less. The heat resistance is remarkably improved when it is preferably 20 J / g or less, more preferably 10 J / g or less, and even more preferably less than 1 J / g.

Moreover, in this invention, it is preferable that the degree of crystallization of the polylactic acid resin in a molded object is high. As the degree of crystallization of the polylactic acid resin in the molded article, the value of the formula represented by the following formula (2), that is, the total amount of enthalpy is 20 J / g or more, preferably 30 J / g or more, more preferably When it is 40 J / g or more, it can be determined that the polylactic acid resin is crystallized in the molded body, and if this value is 20 J / g or more, preferably 30 J / g or more, more preferably 40 J / g or more, molding is performed. The heat resistance of the body is remarkably improved.
ΔHc1d + ΔHc2u (2)
[In the formula, ΔHc1d represents the crystallization enthalpy at the time of cooling of the polylactic acid resin measured in the first time, and ΔHc2u represents the crystallization enthalpy at the time of temperature rising of the polylactic acid resin measured in the second time. ]

  Here, ΔHc1d and ΔHc2u can be obtained from a thermal measurement by DSC, and 10 mg of a sample cut out from the molded body, in a nitrogen atmosphere, as a first measurement, from 30 ° C. to 200 ° C. at a temperature rising rate of 20 ° C./min. After the temperature was raised to 200 ° C. and held at 200 ° C. for 5 minutes, the temperature was lowered from 200 ° C. to 30 ° C. at a rate of temperature drop of 20 ° C./minute, held at 30 ° C. for 1 minute, and then, as the second measurement, the rate of temperature rise The temperature is measured by raising the temperature from 30 ° C. to 200 ° C. at 20 ° C./min, holding at 200 ° C. for 5 minutes, and then lowering the temperature from 200 ° C. to 30 ° C. at a temperature lowering rate of 20 ° C./min. In this measurement, the crystallization enthalpy of the polylactic acid resin observed when the temperature of the first measurement is lowered corresponds to ΔHc1d, and the crystallization enthalpy of the polylactic acid resin observed when the temperature of the second measurement is raised corresponds to ΔHc2u. .

  The method for producing the molded body of the present invention is not particularly limited, and any generally performed molding method such as injection molding, extrusion molding, blow molding, inflation molding, or vacuum / pressure molding can be applied.

  In the present invention, in order to obtain a molded product that is transparent and the ratio of crystallization represented by the above formula (1) is within the range specified in the present invention, for example, the polylactic acid resin and the polyacetal resin, as necessary. A method in which a resin composition formed by blending an amide compound which is an optional component is molded, and then heat-treated in a temperature range from the glass transition temperature (Tg) of the polylactic acid resin to the melting point (Tm) of the polylactic acid resin is preferably exemplified. . Here, Tg and Tm mean the value of the polylactic acid resin used for blending. Since the resin composition used in the molded product of the present invention contains a polyacetal resin in the polylactic acid resin, it can be sufficiently crystallized while maintaining excellent transparency even when the molded product is heat-treated. .

  The heat treatment method is a method in which heat treatment is performed at a constant temperature in the temperature range of the glass transition temperature (Tg) to the melting point (Tm) of the polylactic acid resin, and the temperature is raised continuously or at least at two or more stages. Thus, a method such as a heat treatment method can be preferably employed. Among them, from the viewpoints of transparency and heat resistance, a method of performing a heat treatment by heating at a temperature that is continuous or at least at two or more stages is more preferable. A method in which the temperature is continuously increased so that the rate is 0.5 ° C./min, preferably 0.3 ° C./min, more preferably 0.25 ° C./min, or 1 minute, preferably 10 minutes, More preferably, any method such as a method in which the temperature is increased stepwise by 15 minutes, more preferably every 30 minutes at 60 ° C., preferably 40 ° C., more preferably 20 ° C., still more preferably 10 ° C. can be applied. However, from the viewpoint that a molded article excellent in transparency and heat resistance can be obtained, a method in which the temperature is increased stepwise by setting the temperature to at least two stages or more, more preferably three stages or more is preferable.

  About the temperature range of heat processing, Preferably it is a temperature range of Tg + 5 degreeC-Tm-10 degreeC, More preferably, Tg + 7 degreeC-Tm-20 degreeC. Furthermore, when the crystallization temperature (Tc) of the resin composition obtained by blending the polylactic acid resin and the polyacetal resin is lower than Tm-20 ° C., a temperature range of Tg + 7 ° C. to Tc, preferably Tg + 7 ° C. After heat treatment in a temperature range of Tc-5 ° C, more preferably Tg + 7 ° C to Tc-15 ° C, more preferably Tg + 7 ° C to Tc-30 ° C, Tc or higher, preferably Tc + 5 ° C or higher, more preferably Tc + 10 ° C or higher. It is particularly preferable to raise the temperature stepwise such as heat treatment. When the temperature of the heat treatment is lower than Tg, it is hardly crystallized, and when it is higher than Tm, it is difficult to obtain a transparent and crystallized molded body even if the crystallization time is shortened.

  The heat treatment time is not particularly limited as long as the molded body is sufficiently crystallized, but it is at least 10 seconds or more, more preferably 1 minute or more, more preferably 10 minutes or more, particularly preferably. It takes 30 minutes or more, and if it is heat-treated for about 1 hour, it is sufficiently crystallized.

  For the resin composition forming the molded article of the present invention, fillers (glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers, glass flakes, glass beads, glass beads, Ceramic fiber, ceramic beads, asbestos, wollastonite, talc, clay, mica, sericite, zeolite, bentonite, montmorillonite, synthetic mica, dolomite, kaolin, fine silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, Magnesium carbonate, Barium sulfate, Calcium oxide, Aluminum oxide, Titanium oxide, Aluminum silicate, Silicon oxide, Gypsum, Novacurite, Dawsonite and clay, stabilizers (hindered phenols, benzotriazoles, benzophenones, benzoates) UV absorbers and antioxidants such as cyanoacrylates and cyanoacrylates), lubricants or plasticizers (higher fatty acids, acid esters and acid amides, and higher alcohols), mold release agents (montanic acid and salts thereof, esters thereof) , Its half esters, stearyl alcohol, stellar amide, ethylene wax, etc.), discoloration inhibitor (phosphite, hypophosphite, etc.), flame retardant (halogen flame retardant, phosphorus or silicone non-halogen) Flame retardants, etc.), colorants including dyes and pigments, crystal nucleating agents (talc, organic carboxylic acid metal salts, etc.) and additives such as antistatic agents may be included. These additives can be used alone or in combination of two or more.

  Further, other thermoplastic resins (for example, polyethylene, polypropylene, acrylic resin, polyamide, polyphenylene sulfide resin, polyether ether) can be used for the resin composition forming the molded article of the present invention within a range not to impair the purpose of the present invention. Ketone resins, polyesters, polysulfones, polyphenylene oxides, polyimides and polyetherimides) and thermosetting resins (eg phenolic resins, melamine resins, polyester resins, silicone resins and epoxy resins) and soft thermoplastic resins (eg ethylene / glycidyl) Methacrylate copolymer, polyester elastomer, polyamide elastomer, ethylene / propylene terpolymer, ethylene / butene-1 copolymer, and the like. Rukoto can.

  In the present invention, the method for producing the resin composition is not particularly limited. For example, after pre-blending a polylactic acid resin and a polyacetal resin, an optional amide compound, or other additives, if necessary, Above the melting point, a method of uniformly kneading with a single or twin screw extruder or a method of removing the solvent after mixing in a solution is preferably used.

  Examples of the molded product of the present invention include injection molded products, extrusion molded products, blow molded products, films and sheets. From the viewpoint of fully utilizing the effects of the present invention, the molded body preferably has a portion having a thickness of 20 μm or more, particularly preferably a molded body having a portion of 100 μm or more, and a molded body having a portion of 1 mm or more. It is preferable that Furthermore, from the viewpoint of fully utilizing the transparency, the molded body preferably has a portion having a thickness of 20 μm to 3 mm, more preferably a molded body having a portion of 20 μm to 2 mm, and 20 μm to 1.5 mm. More preferably, the molded body has a portion.

  In addition, the molded object of this invention can be obtained as a molded object which was fully excellent in transparency and heat resistance, without carrying out an extending | stretching process, and thickness is 100 micrometers or more, Preferably it is 500 micrometers or more, More preferably, it is 1 mm or more. It can be used as an unstretched film and sheet. Although the upper limit of the thickness of a molded object is not specifically limited, 3 mm or less is preferable, 2 mm or less is more preferable, and 1.5 mm or less is further more preferable.

  Further, the molded article, film, sheet and fiber of the present invention can be used for various applications such as electric / electronic parts, building members, automobile parts, various packaging materials and daily necessities.

  Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. Here, the number of parts in the examples indicates parts by weight.

  The various characteristics in the examples were evaluated according to the methods described below.

[transparency]
Using a Nippon Denshoku haze meter NDH-300A, according to JIS-K7105, the haze of the sample cut into 3 cm squares in the vertical and horizontal directions was measured.

[Ratio of crystallization]
Using a Perkin-Elmer DSC7, 10 mg of a sample cut out from the molded product was heated from 30 ° C. to 200 ° C. at a heating rate of 20 ° C./min in a nitrogen atmosphere, and the resulting crystallization enthalpy (ΔHc ) And crystal melting enthalpy (ΔHm), the ratio of crystallization was determined from the following formula (1).
[(ΔHm−ΔHc) / ΔHm] × 100 (1)
[In the formula, ΔHm represents the crystal melting enthalpy of the molded body, and ΔHc represents the crystallization enthalpy at elevated temperature of the molded body. ]

Further, in Examples 14 to 21 and Comparative Examples 4 to 6, in addition to the above measurement, as a first measurement in a nitrogen atmosphere, 10 mg of a sample cut from a molded product using DSC7 manufactured by PerkinElmer After raising the temperature from 30 ° C. to 200 ° C. at a temperature rate of 20 ° C./minute, holding at 200 ° C. for 5 minutes, then lowering the temperature from 200 ° C. to 30 ° C. at a temperature reduction rate of 20 ° C./minute, and holding at 30 ° C. for 1 minute As a second measurement, the temperature was increased from 30 ° C. to 200 ° C. at a temperature increase rate of 20 ° C./min, held at 200 ° C. for 5 minutes, and then decreased from 200 ° C. to 30 ° C. at a temperature decrease rate of 20 ° C./min. Using the obtained crystallization enthalpy (ΔHc1d) of the polylactic acid resin observed at the time of temperature decrease in the first measurement and the crystallization enthalpy (ΔHc2u) of the polylactic acid resin observed at the time of temperature increase in the second measurement From the formula (2), the state of crystallization of the polylactic acid resin was evaluated. It is judged that the one where the value calculated | required by following formula (2) is many has crystallized more the polylactic acid resin in a molded object.
ΔHc1d + ΔHc2u (2)
[In the formula, ΔHc1d represents the crystallization enthalpy at the time of cooling of the polylactic acid resin measured in the first time, and ΔHc2u represents the crystallization enthalpy at the time of temperature rising of the polylactic acid resin measured in the second time. ]

[Heat-resistant]
The obtained molded product or the cut sample was horizontally supported at one end in a hot air dryer, and the temperature at which the tip of the molded product drooped was measured by gradually raising the temperature, and was defined as the thermal deformation temperature.

[Comparative Examples 1-3]
Poly-L lactic acid resin having a D-form content of 2%, a PMMA equivalent weight average molecular weight of 170,000, a glass transition temperature of 60 ° C. and a melting point of 170 ° C., and a melt index value measured at 190 ° C. of 27 g / A polyacetal copolymer having a melting point of 170 ° C. for 10 minutes (Amilas S731 manufactured by Toray Industries, Inc.) was mixed in the proportions shown in Table 1, respectively, and a 40 mm diameter single screw extruder with a cylinder temperature of 200 ° C. and a rotation speed of 50 rpm. A resin composition was obtained by performing melt kneading under conditions.

The obtained resin composition was molded using an injection molding machine at a cylinder temperature of 200 ° C. and a mold temperature of 20 ° C. to produce a sheet-like molded product having a thickness of 1 mm × length of 10 cm × width of 10 cm. The conversion rate, haze, and heat distortion temperature were measured. Furthermore, after heat-treating this sheet on the following conditions using the hot air dryer, the ratio of crystallization, haze, and heat-deformation temperature were measured. The results are also shown in Table 1.
Heat treatment method a: 20 minutes at 70 ° C. → 20 minutes at 90 ° C. → 10 minutes at 110 ° C. Heat treatment method b: 35 minutes at 80 ° C. → 15 minutes at 140 ° C. Heat treatment method c: 50 minutes at 110 ° C.

  As is apparent from the results in Table 1, a molded article comprising a resin composition obtained by blending the polylactic acid resin and the polyacetal resin of the present invention is a transparent and crystallized molded article excellent in transparency and heat resistance. I understand that.

[Examples 1-8, Comparative Examples 4-6]
Poly-L lactic acid resin having a D-form content of 2%, a PMMA equivalent weight average molecular weight of 170,000, a glass transition temperature of 60 ° C. and a melting point of 170 ° C., and a melt index value measured at 190 ° C. of 27 g / A polyacetal copolymer having a melting point of 170 ° C. for 10 minutes (Amilas S731 manufactured by Toray Industries) and the amide compound shown in Table 2 were mixed in the proportions shown in Table 2, respectively, and a temperature of 200 mm was obtained using a single screw extruder having a diameter of 40 mm. A resin composition was obtained by performing melt kneading under conditions of ° C and a rotation speed of 50 rpm.

The amide compounds used here are as follows. A to D were obtained by reacting a corresponding carboxylic acid chloride and an amine compound according to a known method.
A: terephthalic acid dianilide B: trimesic acid tris (t-butylamide)
C: 1,4-cyclohexanedicarboxylic acid dianilide D: N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane E: Ethylene bislauric acid amide (Nihon Kasei Slipax L)

The obtained resin composition was molded using an injection molding machine at a cylinder temperature of 200 ° C. and a mold temperature of 20 ° C. to produce a molded body having a thickness of 1 mm × length of 10 cm × width of 10 cm, and the ratio of crystallization, haze, The heat distortion temperature was measured. Furthermore, this molded body was heat-treated using a hot air dryer under the following conditions, and then the crystallization ratio, haze, and heat distortion temperature were measured. The results are also shown in Table 3.
Heat treatment method a: 15 minutes at 70 ° C. → 15 minutes at 90 ° C. → 10 minutes at 110 ° C. Heat treatment method b: 40 minutes at 110 ° C.

  As is apparent from the results in Table 2, a molded product comprising a resin composition comprising a polylactic acid resin, a polyacetal resin, and an amide compound is excellent in transparency and heat resistance, and is a sufficiently crystallized molded product. I know that there is.

Claims (8)

The total lactic acid component is transparent and comprises a resin composition comprising a polylactic acid resin containing 80% or more of L-form or 80% or more of D-form, a polyacetal resin and an amide compound. ) Is a molded body in which the ratio of crystallization of the molded body is 60% or more, and the polylactic acid resin and the polyacetal resin are compatible in the molded body.
[(ΔHm−ΔHc) / ΔHm] × 100 (1)
[In the formula, ΔHm represents the crystal melting enthalpy of the molded body, and ΔHc represents the crystallization enthalpy at elevated temperature of the molded body. ] The molded product according to claim 1, wherein the total amount of the polylactic acid resin and the polyacetal resin is 100 to 60 parts by weight when the total amount is 100 parts by weight. The molded article according to claim 1 or 2, wherein the amount of the amide compound is 0.1 to 10 parts by weight when the total of the polylactic acid resin and the polyacetal resin is 100 parts by weight. The molded product according to any one of claims 1 to 3, wherein the amide compound is at least one selected from alicyclic amides and aromatic amides. The amide compound is at least one selected from N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane, trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, and terephthalic acid dianilide. It is a seed | species, The molded object of any one of Claims 1-4. The molded product according to any one of claims 1 to 5, which has a portion having a thickness of 20 µm or more and a haze value of 30% or less. The molded product according to any one of claims 1 to 5, which has a portion having a thickness of 1 mm or more and a haze value of 20% or less. 8. The polylactic acid resin according to any one of claims 1 to 7, wherein the polylactic acid resin is a polylactic acid resin containing 98% or more of L-form or 98% or more of D-form among total lactic acid components. The molded body described.