JP2007254587A - Resin composition and molding comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition that comprises a biodegradable polymer, has excellent moldability and mechanical properties, generates a small amount of formaldehyde during molding or from a molding and has extremely excellent mold deposit properties and a molding composed of the same. <P>SOLUTION: The resin composition is obtained by mixing a resin composition comprising 100 parts.wt. of the total of a polylactic acid resin (A) and a polyacetal resin (B) with 0.01-3 parts.wt. of a carboxylic acid metal salt that is a carboxylic acid metal salt containing at least one group selected from the group consisting of a hydroxy group, a formyl group, an amino group, an ester group and an alkoxy group and has a property in which the carboxylic acid metal salt is reacted with formic acid to form a carboxylic acid and the carboxylic acid obtained by reaction with formic acid is cyclized by (i) condensation polymerization and/or (ii) self-condensation and 0.03-0.08 part.wt. of a hydrazide compound (D). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition containing a biodegradable polymer, excellent in moldability and mechanical properties, having a small amount of formaldehyde generated during molding and from a molded product, and having extremely excellent mold depositing properties, and the resin composition It is related with the molded article which consists of.

  In recent years, the problem of depletion of fossil resources such as petroleum has been highlighted, and biopolymers made of resin derived from plant resources have attracted attention as plastic materials. Among these, lactic acid, which is a monomer of polylactic acid resin, is manufactured at low cost by a fermentation method using microorganisms from plant resources such as corn and sweet potato, and has a high melting point of about 170 ° C., and can be melt-molded. It is expected to be a practically excellent biodegradable polymer.

  However, since the polylactic acid resin has a low crystallization speed, there is a limit to use it as a molded product after crystallization. For example, when polylactic acid resin is injection-molded, there have been practically significant problems such as requiring a long molding cycle time and heat treatment after molding, and large deformation during molding and heat treatment. In addition, polylactic acid resins have problems in heat resistance and weather resistance, particularly long-term heat resistance, and there has been a problem that strength is greatly reduced when used for a long time at high temperature. For the purpose of improving long-term heat resistance and weather resistance, Patent Document 1 discusses stabilizers and weathering agents, but their effects are insufficient.

  In order to solve these problems, Patent Document 2 discloses excellent moldability, mechanical properties, heat resistance, etc. by blending a mixture of polylactic acid resin and polyacetal resin with a hydrazide compound as a formaldehyde scavenger and further an antioxidant. Is disclosed. However, in this method, the amount of formaldehyde generated at the time of molding and from the molded product has not been reduced so much, and the amount of the stabilizer is not appropriate. Therefore, when injection molding is performed, the stabilizer component adheres to the mold surface, and the mold deposit Not good.

  On the other hand, polyacetal resin is widely used in automotive parts, electrical / electronic equipment parts, general functional parts, etc., because it has excellent mechanical properties, heat resistance, lubricity, and chemical resistance in a balanced manner. Recently, generation of volatile organic compounds (VOC) from molded articles has been reduced, and more specifically, suppression of formaldehyde generated by thermal decomposition, ultraviolet decomposition or the like in a polyacetal resin, which is a polymer of formaldehyde, has been demanded. Especially in automobile interior parts, home appliance parts, precision electrical / electronic equipment parts, offices, office buildings, private houses, indoor functional parts of apartment buildings, and decorative parts, the usage environment is affected by sunlight. In some cases, the temperature may be high or ultraviolet rays may be struck, and there is a need to reduce the occurrence of VOCs in a sealed room / device with a limited volume.

In order to solve these problems, Patent Document 3 discloses that polyacetal resin contains a specific carboxylic acid metal salt and melamine or an antioxidant as a heat stabilizer, thereby reducing the amount of formaldehyde generated during molding or heating. And improved thermal stability. However, although this method can reduce the amount of formaldehyde generated to some extent, it is still not sufficient as a countermeasure against sick house syndrome, and a polymer derived from plant resources is not used.
JP-A-6-184417 JP 2003-321601 A JP 2005-330463 A

  An object of the present invention is a resin composition containing a biodegradable polymer, excellent in moldability and mechanical properties, having a small amount of formaldehyde generated at the time of molding or from a molded product, and extremely excellent in mold depositing property, and The provision of molded products.

  In order to achieve the above object, the resin composition of the present invention is a metal salt of carboxylic acid with respect to the resin composition in which the total of the polylactic acid resin (A) and the polyacetal resin (B) is 100 parts by weight. And 0.01 to 3 parts by weight of a metal salt (C) of a carboxylic acid having a property of reacting with formic acid to form a carboxylic acid, and the carboxylic acid is cyclized by condensation polymerization and / or self-condensation The hydrazide compound (D) is blended in an amount of 0.01 to 0.08 parts by weight.

That is, the present invention is as follows.
(1) For the resin composition in which the total of the polylactic acid resin (A) and the polyacetal resin (B) is 100 parts by weight, the resin composition is further selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group, and an alkoxyl group. A metal salt of a carboxylic acid having at least one group, and reacts with formic acid to form a carboxylic acid, and the carboxylic acid reacted with formic acid undergoes (i) polycondensation and / or (ii) self-condensation. A resin composition comprising 0.01 to 3 parts by weight of a metal salt (C) of a carboxylic acid having a property of being cyclized and 0.03 to 0.08 parts by weight of a hydrazide compound (D),
(2) The blending amount of the polylactic acid resin (A) is 10 parts by weight or more and 99 parts by weight or less with respect to a total of 100 parts by weight of the polylactic acid resin (A) and the polyacetal resin (B) ( 1) The resin composition according to
(3) The resin composition according to (1) or (2), wherein the metal salt of carboxylic acid (C) is a metal salt of carboxylic acid represented by the following general formula (I):

(In the formula, R1 and R2 are a hydrogen atom and an organic group having 10 or less carbon atoms, which may be the same or different, and m, n and m + n are each an integer from 0 to 5, X represents a group selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group and an alkoxyl group.
(4) The carboxylic acid represented by the general formula (I) is glycolic acid, lactic acid, 3-hydroxypropionic acid, α-hydroxyisobutyric acid, β-hydroxyisobutyric acid, malic acid, citric acid, tartaric acid, aminoacetic acid The resin composition according to (3), which is at least one selected from the group consisting of 2-amino-propionic acid, 3-aminopropionic acid, 2-amino-butyric acid, glutamic acid, L-alanine and β-alanine,
(5) The antioxidant (E) is further blended in an amount of 0.01 to 3 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin (A) and the polyacetal resin (B). A molded article comprising the resin composition according to any one of the above and (6) the resin composition according to any one of (1) to (5).

  According to the present invention, as described below, it is possible to obtain a resin composition that is excellent in moldability and mechanical properties, has a small amount of formaldehyde generated during molding and from a molded product, and is extremely excellent in mold depositability.

  The polylactic acid resin (A) used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Other copolymerization components include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, Glycol compounds such as pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalate Acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid Dicarboxylic acids such as 5-sodium sulfoisophthalic acid and 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, and caprolactone, Examples include lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. As such a copolymer component, it is preferable to set it as content of 30 mol% or less normally in all the monomer components, and it is preferable that it is 10 mol% or less.

  In the present invention, it is preferable to use a polylactic acid resin (A) having a high optical purity of the lactic acid component from the viewpoint of compatibility. That is, it is preferable that 70% or more of the L isomer or 70% or more of the D isomer is included in the total lactic acid component of the polylactic acid resin (A), and 80% or more of the L isomer is contained or the D isomer is contained. More preferably, 80% or more is contained, 90% or more of L isomer or 90% or more of D isomer is further included, 95% or more of L isomer or 95% or more of D isomer is contained. It is particularly preferable that the L-form is contained in 98% or more or the D-form is contained in 98% or more. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  The molecular weight and molecular weight distribution of the polylactic acid resin (A) are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more. Furthermore, it is desirable that it is 80,000 or more. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  The melting point of the polylactic acid resin (A) 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 (A) 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% of the D form. The polylactic acid resin (A) having a melting point of 150 ° C. or higher is contained in the polylactic acid having a melting point of 160 ° C. or higher because the L isomer is contained in 95% or more or the D isomer is contained in 95% or more. Can be obtained by containing 98% or more of L-form or 98% or more of D-form.

  As a method for producing such a polylactic acid resin (A), 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 homopolymer or copolymer having an oxymethylene unit. However, in the present invention, the oxyalkylene mainly comprises oxymethylene units and has 2 to 8 adjacent carbon atoms in the main chain. Preference is given to using acetal copolymers containing no more than 15% by weight of units.

  As an example of a typical method for producing an acetal 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, a method of producing by deactivating the catalyst and stabilizing the end group, or without using any solvent, into the self-cleaning type agitator, Examples thereof include a method in which trioxane, a copolymerization component and a catalyst are introduced and bulk polymerization is performed, and then the unstable terminal is further decomposed and removed.

  The viscosity of these polymers is not particularly limited as long as it can be used as a molding material, but the melt flow rate (MFR) can be measured by the ASTM D1238 method, and the temperature is 190 ° C. and the measurement load is 2,160 g. The MFR measured below is preferably in the range of 0.1 to 100 g / 10 min, particularly preferably in the range of 1.0 to 50 g / 10 min.

      The metal salt (C) of the carboxylic acid used in the polyoxymethylene resin composition of the present invention has at least one group selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group and an alkoxyl group. It is a metal salt of a carboxylic acid, and reacts with formic acid to form a carboxylic acid, and the carboxylic acid reacted with formic acid has the property of (i) condensation polymerization and / or (ii) self-condensation to cyclize The metal salt of carboxylic acid (C) is used.

  Hereinafter, such a metal salt of a carboxylic acid may be simply referred to as a metal salt (C) of a carboxylic acid.

  The metal salt of (C) carboxylic acid is preferably a metal salt of carboxylic acid represented by the following general formula (I).

(In the formula, R1 and R2 are a hydrogen atom and an organic group having 10 or less carbon atoms, which may be the same or different, and m, n and m + n are each an integer from 0 to 5, X represents a group selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group and an alkoxyl group.)
Here, X is a group selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group, and an alkoxyl group, and among them, a hydroxyl group and an amino group are preferable. Specific examples of X include hydroxyl group, formyl group, amino group, methyl ester group, ethyl ester group, propyl ester group, butyl ester group, pentyl ester group, hexyl ester group, methoxy group, ethoxy group, propoxy group, butoxy group, Examples thereof include a pentyloxy group and a hexyloxy group, and among them, a hydroxyl group and an amino group are preferable. R1 and R2 are a hydrogen atom and an organic group having 10 or less carbon atoms, and these may be the same or different. Specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, pentyl Group, hexyl group, amino group, and carboxyl group. Among them, a hydrogen atom, a methyl group, an amino group, and a carboxyl group are preferable. M and n each represent an integer from 0 to 5, preferably an integer from 0 to 2. Furthermore, m + n is an integer from 0 to 5, and is preferably an integer from 0 to 4. Thus, by selecting X, R1, and R2, and by setting m and n to the numbers in the above range, the carboxylic acid can easily exhibit the properties of condensation polymerization or self-condensation and cyclization. preferable.

  Preferred examples of the carboxylic acid represented by the general formula (I) include aliphatic hydroxycarboxylic acids, alicyclic hydroxycarboxylic acids, and aromatic hydroxycarboxylic acids. Of these, aliphatic hydroxycarboxylic acids are particularly preferred.

  Specific examples of the aliphatic hydroxycarboxylic acid include monohydroxymonocarboxylic acid, monohydroxydicarboxylic acid, monohydroxytricarboxylic acid, dihydroxymonocarboxylic acid, dihydroxydicarboxylic acid, dihydroxytricarboxylic acid, trihydroxymonocarboxylic acid, and trihydroxydicarboxylic acid. Preferred examples include acid and trihydroxytricarboxylic acid. Specific compounds are exemplified below.

  Monohydroxymonocarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, α-hydroxy-n-butyric acid, α-hydroxyisobutyric acid, α-hydroxy-n-valeric acid, α-hydroxyisovaleric acid, 2 -Hydroxy-2-methylbutanoic acid, α-hydroxy-n-caproic acid, α-hydroxyisocaproic acid, 2-ethyl-2-hydroxybutanoic acid, 2-hydroxy-2-methylpentanoic acid, 2-hydroxy-2- Methylhexanoic acid, 2-hydroxy-2,4-dimethylpentanoic acid, hydroacrylic acid, β-hydroxybutyric acid, β-hydroxyisobutyric acid, β-hydroxy-n-valeric acid, β-hydroxyisovaleric acid, α-ethyl Examples include hydroacrylic acid, α-hydroxyacrylic acid, vinyl glycolic acid, and propenyl glycolic acid.

  As monohydroxydicarboxylic acid, hydroxymalonic acid, isomalic acid, 1-hydroxypropane-1,1-dicarboxylic acid, 1-hydroxybutane-1,1-dicarboxylic acid, 1-hydroxy-2-methylpropane-1,1 -Dicarboxylic acid, 2-hydroxyethane-1,1-dicarboxylic acid, 2-hydroxy-3-methylpropane-1,1-dicarboxylic acid, 1- (hydroxymethyl) propane-1,1-dicarboxylic acid, malic acid, α-methylmalic acid, α-hydroxy-α'-methylsuccinic acid, α-hydroxy-α ', α'-dimethylsuccinic acid, α-hydroxy-α, α'-dimethylsuccinic acid, α-hydroxy-α'- Ethyl succinic acid, α-hydroxy-α'-methyl-α-ethyl succinic acid, trimethylmalic acid, α-hydroxyglutaric acid, β-hydride Kishigurutaru acid, beta-hydroxy -β- methyl glutaric, beta-hydroxy-.alpha., alpha-dimethyl glutaric acid, alpha-hydroxy slip down acid, alpha-hydroxy sebacate.

  Examples of monohydroxytricarboxylic acid include citric acid and isocitric acid.

  Examples of the dihydroxy monocarboxylic acid include glyceric acid, 2,3-dihydroxybutanoic acid, 2,3-dihydroxy-2-methylpropionic acid, 3-hydroxy-2-hydroxymethylpropionic acid, 3,4-dihydroxybutanoic acid, 2 , 4-dihydroxy-3,3-dimethylbutanoic acid, 2,3-dihydroxy-2- (1′-methylethyl) butanoic acid.

  Examples of the dihydroxydicarboxylic acid include tartaric acid, methyltartaric acid, dimethyltartaric acid, α, β-dihydroxyglutaric acid, α, γ-dihydroxyglutaric acid, α, γ-dihydroxy-β-methylglutaric acid, α, γ-dihydroxy-β- Ethyl-β-methylglutaric acid, α, γ-dihydroxy-α, γ-dimethylglutaric acid, α, δ-dihydroxyadipic acid, β, γ-dihydroxyadipic acid, 2,5-dihydroxy-5-isopropyl-2- Examples include methylhexanedioic acid, dihydroxyfumaric acid, and dihydroxymaleic acid.

  Examples of the dihydroxytricarboxylic acid include 1,2-dihydroxyethane-1,2,2-tricarboxylic acid, 1,2-dihydroxypropane-1,2,3-tricarboxylic acid, and 1,3-dihydroxypropane-1,1,3. -Tricarboxylic acids.

  Examples of the trihydroxymonocarboxylic acid include trihydroxybutyric acid, trihydroxyisobutyric acid, and 3,4,5-trihydroxyhexanoic acid. Examples of trihydroxydicarboxylic acid include trihydroxyglutaric acid.

  The carboxylic acid represented by the general formula (I) is particularly preferably glycolic acid, lactic acid, 3-hydroxypropionic acid, α-hydroxyisobutyric acid, β-hydroxyisobutyric acid, malic acid, citric acid, and tartaric acid. Of these, malic acid, citric acid and tartaric acid are preferred. These may be used alone or in combination of two or more.

  The carboxylic acid represented by the general formula (I) is also preferably a carboxylic acid having an amino group, among which aminoacetic acid, 2-amino-propionic acid, 3-aminopropionic acid or 2-amino- Butyric acid, glutamic acid, L-alanine, and β-alanine are preferred.

  In the resin composition of the present invention, the metal constituting the metal salt (C) of the carboxylic acid is preferably an alkali metal, an alkaline earth metal, aluminum, zinc, manganese, iron, or silver. Examples include lithium, rubidium, cesium, potassium, and sodium. Examples of the alkaline earth metal include calcium, magnesium, beryllium, strontium, and barium, and among these, calcium, magnesium, potassium, and sodium are more preferable.

  The metal salt (C) of the carboxylic acid used in the resin composition of the present invention is preferably a metal salt of an aliphatic hydroxycarboxylic acid, a metal salt of an alicyclic hydroxycarboxylic acid, a metal salt of an aromatic hydroxycarboxylic acid, and Examples thereof include a metal salt of a carboxylic acid having an amino group. Among these, a metal salt of an aliphatic hydroxycarboxylic acid is particularly preferable. Specifically, calcium lactate, magnesium lactate, sodium lactate, potassium lactate, sodium glycolate, sodium malate, potassium malate, calcium malate, calcium citrate, trisodium citrate, tripotassium citrate, hydrogen citrate Suitable examples include disodium, dipotassium hydrogen citrate, sodium dihydrogen citrate, potassium dihydrogen citrate, calcium tartrate, sodium tartrate, potassium tartrate, sodium hydrogen tartrate, potassium hydrogen tartrate, and sodium potassium tartrate. it can. More preferably, calcium lactate, magnesium lactate, sodium lactate, potassium lactate, sodium glycolate, sodium malate, potassium malate, calcium citrate, trisodium citrate, tripotassium citrate, calcium tartrate, sodium hydrogen tartrate, tartaric acid Sodium and potassium hydrogen tartrate, especially when using sodium lactate, sodium malate, potassium malate, trisodium citrate, tripotassium citrate, sodium tartrate, no deterioration of mechanical properties, color and thermal stability An excellent resin composition can be obtained.

  In the resin composition of the present invention, the amount of the carboxylic acid metal salt (C) added is 0.01 to 3 parts by weight with respect to 100 parts by weight of the total of the polylactic acid resin (A) and the polyacetal resin (B). Preferably it is 0.01-2 weight part, Most preferably, it is 0.03-1 weight part. If it is less than 0.001 part by weight, the improvement of the thermal stability is insufficient, and if it exceeds 3 parts by weight, the resin composition is decomposed and foamed, and the stability is impaired.

  Furthermore, in this invention, a hydrazide compound (D) is used as a formaldehyde scavenger. Examples of the hydrazide compound include hydrazide compounds such as monocarboxylic acid hydrazide, dicarboxylic acid monohydrazide, dicarboxylic acid dihydrazide, and polycarboxylic acid polyhydrazide. Among them, monocarboxylic acid dihydrazide and dicarboxylic acid dihydrazide are preferable.

  Specific examples of the monocarboxylic acid dihydrazide include carbonyl dihydrazide. Specific examples of the dicarboxylic acid dihydrazide include adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide.

  Of these, sebacic acid dihydrazide is particularly preferred. These compounds can be used alone or in combination of two or more.

  In the present invention, the blending amount of the hydrazide compound (D) is important, and is 0.03 to 0.08 parts by weight, preferably 0 with respect to 100 parts by weight of the total of the polylactic acid resin (A) and the polyacetal resin (B). 0.05 to 0.08 parts by weight. If the blending amount of the hydrazide compound (D) is less than the above range, the action of capturing formaldehyde generated by heating is insufficient, and if it exceeds the above range, it is not preferable because it adheres to the mold as a mold deposit during molding.

  The resin composition of the present invention may further contain an antioxidant (E). Examples of the antioxidant used in the present invention include hindered phenol compounds, phosphite compounds, thioether compounds, vitamin compounds, and the like.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 '-T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol- Bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) -propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl-5- Til-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3 -(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N ′ -Bis-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionylhexamethylenediamine, N, N'-tetramethylene-bis-3- (3'-methyl-5'- t-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] hydra , N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylene Bis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. Preferably, triethylene glycol-bis- [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] Methane, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], pentaerythrityl-tetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide). Specific product names of hindered phenol compounds include “Adeka Stub” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, manufactured by Asahi Denka Kogyo Co., Ltd. AO-330, “Irganox” 245,259,565,1010,1035,1076,1098,1222,1330,1425,1520,3114,5057 manufactured by Ciba Specialty Chemicals, Sumitomo Chemical's “Smilizer” BHT-R, Examples thereof include MDP-S, BBM-S, WX-R, NW, BP-76, BP-101, GA-80, GM, GS, “Cyanox” CY-1790 manufactured by Cyanamid.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, tetrakis ( 2,4-di-t-butylphenyl) 4,4′-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-) t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl) -6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butyl-phenyl) Nyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkyl phosphite) and the like, and tris (2, 4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) Pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite and the like can be preferably used. Specific product names of the phosphite compounds include “ADK STAB” PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A manufactured by Asahi Denka Kogyo Co., Ltd. 329A, 1178, 1500, C, 135A, 3010, TPP, “Irgaphos” 168 from Ciba Specialty Chemicals, “Smilizer” P-16 from Sumitomo Chemical, “Sand Stub” from Clariant P-EPQ, GE “Weston” 618, 619G, 624 and the like.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropioate). Nate), pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis ( 3-stearylthiopropionate) and the like. Specific product names of thioether compounds include "Adeka Stub" A0-23, AO-412S, AO-503A from Asahi Denka Kogyo Co., Ltd., "Irganox" PS802 from Ciba Specialty Chemicals, and "Sumilyzer" from Sumitomo Chemical. Examples include TPL-R, TPM, TPS, TP-D, Yoshitomi's DSTP, DLTP, DLTOIB, DMTP, Cypro Kasei's “Sinox” 412S, and Cyamide's “Sianox” 1212.

  Specific examples of the vitamin compound include d-α-tocopherol acetate, d-α-tocopherol succinate, d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol, d-δ-tocopherol, d- Natural products such as α-tocotrienol, d-β-tocofetrienol, d-γ-tocofetrienol, d-δ-tocofetrienol, dl-α-tocopherol, dl-α-tocopherol acetate, succinic acid Synthetic products such as dl-α-tocopherol calcium and dl-α-tocopherol nicotinate can be mentioned. Specific product names of vitamin antioxidants include “Tocopherol” from Eisai Co., “Irganox” E201 from Ciba Specialty Chemicals, and the like.

In this invention, as a compounding quantity of antioxidant (E), 0.01-3 weight part with respect to a total of 100 weight part of a polylactic acid resin (A) and a polyacetal resin (B), Preferably 0.05- 1 part by weight, more preferably 0.05 to 0.3 part by weight. If the amount is less than 0.01 parts by weight, the thermal stability is not sufficiently improved, so formaldehyde is likely to be generated during molding. If the amount exceeds 3 parts by weight, the surface of the molded product is bleed out and the appearance is impaired. It is not preferable because it decreases.
Further, the resin composition of the present invention is a glass fiber, carbon fiber, aramid fiber, inorganic filler, organic reinforcing agent, nucleating agent, plasticizer, release agent, light stabilizer, as long as the effects of the present invention are not impaired. Additives such as pressure-sensitive adhesives, lubricants such as metal soaps, hydrolysis resistance improvers, and adhesion aids can be optionally blended.

  Further, for the resin composition of the present invention, other thermoplastic resins (for example, polyolefins such as polyethylene and polypropylene, polyamides, acrylic resins, polyphenylene sulfide resins, and polyetheretherketone resins are used as long as the object of the present invention is not impaired. Polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, etc.) and thermosetting resins (eg phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin etc.) and soft thermoplastic resins (eg ethylene / glycidyl methacrylate) Polymer, ethylene / propylene terpolymer, soft polyolefin polymer such as ethylene / butene-1 copolymer, polyester elastomer, polyamide elastomer, etc.) It may further contain.

  In the resin composition of the present invention, when the total amount of the polylactic acid resin and the polyacetal resin is 100 parts by weight, the blending amount of the polylactic acid resin is preferably 10 to 99 parts by weight, and 30 to 99 parts by weight. It is more preferable that it is 50 to 99 parts by weight. By setting it as such a range, the effect which was further excellent in a moldability and a mechanical characteristic can be expressed.

  The method for producing the resin composition of the present invention is not particularly limited. For example, polylactic acid resin (A), polyacetal resin (B), metal salt of carboxylic acid (C), hydrazide compound (D), and as necessary Depending on the method, the antioxidant (E) and other additives are pre-blended and then melted and kneaded uniformly with a single or twin screw extruder above the melting point, or the solvent is removed after mixing in the solution. Etc. are preferably used.

  The resin composition of the present invention contains a biodegradable polymer, is excellent in moldability and mechanical properties, has a small amount of formaldehyde generated during molding and from molded products, and has extremely excellent mold deposit properties. It can be processed into various molded products and used by methods such as injection molding, extrusion molding, and blow molding. The mold temperature for injection molding is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, even more preferably 80 ° C. or higher from the viewpoint of crystallization, while 120 ° C. from the viewpoint of suppressing deformation of the molded product. The following are preferable, 110 degrees C or less is further more preferable, and 100 degrees C or less is still more preferable.

  In addition, examples of the molded product made of the resin composition of the present invention include injection molded products, extrusion molded products, and blow molded products. In addition, these molded products can be used for various applications such as electric / electronic parts, building members, automobile parts, and daily necessities.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention.

The characteristics of the resin composition were determined according to the following method.
(1) Test piece preparation Using an injection molding machine (FKS-80HG, manufactured by Komatsu Ltd.) with a clamping pressure of 80 tons, the molding conditions were a cylinder temperature of 200 ° C, a mold temperature of 80 ° C, and a molding cycle of 60 seconds. ASTM 1 dumbbells and 1/8 inch thick Izod impact test specimens were prepared.
(2) Mold deposit property Using an injection molding machine (FKS-80HG manufactured by Komatsu Ltd.) with a clamping pressure of 80 tons, the cylinder temperature is 240 ° C., the mold temperature is 30 ° C., and the molding cycle is 10 seconds. The square plate was continuously molded until the mold deposit adhered. The molding machine was stopped every 100 shots, the inside of the mold cavity was visually observed, and the number of shots where adhesion of mold deposits was confirmed was defined as mold deposit property.
(3) Amount of formaldehyde generated Formaldehyde generated when the Izod impact test piece obtained by injection molding was placed in a container with excellent heat resistance and purged with nitrogen, sealed and heated in a hot air oven at 65 ° C for 2 hours. The amount was measured with a Kitagawa gas detector tube (manufactured by Komyo Chemical Co., Ltd.).
(4) Tensile strength The test piece obtained by the above injection molding was allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours, and then subjected to a tensile test according to ASTM D638.

  The contents of the polylactic acid resin (A), polyacetal resin (B), metal salt of carboxylic acid (C), formaldehyde scavenger (D), and antioxidant (E) used in Examples and Comparative Examples are shown below.

・ Polylactic acid resin (A)
A poly-L lactic acid resin having a D-form content of 2% and a PMMA-converted weight average molecular weight of 170,000 was used.

・ Polyacetal resin (B)
Amylas S761 manufactured by Toray Industries, Inc., which is a polyacetal copolymer, was used.

-Metal salt of carboxylic acid (C)
Sodium lactate (C-1), calcium citrate (C-2), tripotassium citrate (C-3): all manufactured by Kanto Chemical Co., Inc. were used.

-Alkali metal salt or alkaline earth metal salt of saturated fatty acid 12-hydroxycalcium stearate (C-4): Daiwa Chemical's die wax OHC was used.

-Metal hydroxide Calcium hydroxide (C-5): The thing made by Kanto Chemical Co., Inc. was used.

・ Formaldehyde scavenger (D)
Sebacic acid dihydrazide (D-1), isophthalic acid dihydrazide (D-2), adipic acid dihydrazide (D-3), melamine (D-4): all manufactured by Nippon Hydrazine Kogyo Co., Ltd. were used.

・ Antioxidant (E)
Triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}: Irganox 245 manufactured by Ciba Specialty Chemicals Co., Ltd. was used.

[Examples 1 to 7]
As shown in Examples 1 to 7 shown in Table 1, a specific carboxylic acid metal salt (C) is used for a resin composition comprising 80 parts by weight of a polylactic acid resin (A) and 20 parts by weight of a polyacetal resin (B). -1 to C-3) and hydrazide compounds (D-1 to D-3) are blended in appropriate amounts, so that the mold deposit property is good and the amount of formaldehyde generated can be suppressed extremely low without impairing the mechanical properties. I understand that.

[Comparative Examples 1-6]
In the comparative examples shown in Table 2, in the case other than the metal salt of carboxylic acid (C-4, C-5) and other than the hydrazide compound (D-4), the effect of suppressing formaldehyde generation is insufficient, and the mold Depositability is also low.

  Moreover, when there are too many metal salts of carboxylic acid, resin will decompose | disassemble, as a result, the amount of formaldehyde generation is large, and mold deposit property and mechanical characteristics are falling. On the other hand, if the blending amount of the hydrazide compound is too small, the effect of suppressing the formaldehyde generation is reduced, and if too much, the amount of formaldehyde generated is suppressed, but the mold deposit property is extremely decreased.

[Examples 8 to 12]
In Examples 8 to 12 shown in Table 3, contrary to Examples 1 to 7, a specific carboxylic acid metal salt (20 parts by weight of polylactic acid resin (A) and 80 parts by weight of polyacetal resin (B) ( By blending appropriate amounts of C-2, C-3) and hydrazide compounds (D-1, D-3), the mold depositing property is good and the amount of formaldehyde generated can be suppressed extremely low without impairing the mechanical properties. I understand that.

  Since the resin composition of the present invention is extremely excellent in mold depositing property at the time of molding, it has high production efficiency and contains a biodegradable polymer derived from plant resources. it can. Furthermore, since it is excellent in mechanical properties and has a small amount of formaldehyde generated during molding or from a molded product, it can be used extremely practically and effectively for applications such as electrical / electronic equipment parts and general functional parts.

Claims (6)

  At least one selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group and an alkoxyl group with respect to the resin composition in which the total of the polylactic acid resin (A) and the polyacetal resin (B) is 100 parts by weight. A metal salt of a carboxylic acid having two groups, which reacts with formic acid to form a carboxylic acid, and the carboxylic acid reacted with formic acid is (i) polycondensed and / or (ii) self-condensed to cyclize The resin composition formed by mix | blending 0.01-3 weight part of carboxylic acid metal salt (C) which has the property to do, and 0.03-0.08 weight part of hydrazide compound (D).   The blending amount of the polylactic acid resin (A) is 10 parts by weight or more and 99 parts by weight or less with respect to a total of 100 parts by weight of the polylactic acid resin (A) and the polyacetal resin (B). The resin composition as described. The resin composition according to claim 1 or 2, wherein the metal salt of the (C) carboxylic acid is a metal salt of a carboxylic acid represented by the following general formula (I).

(In the formula, R1 and R2 are a hydrogen atom and an organic group having 10 or less carbon atoms, which may be the same or different, and m, n and m + n are each an integer from 0 to 5, X represents a group selected from the group consisting of a hydroxyl group, a formyl group, an amino group, an ester group and an alkoxyl group.   The carboxylic acid represented by the general formula (I) is glycolic acid, lactic acid, 3-hydroxypropionic acid, α-hydroxyisobutyric acid, β-hydroxyisobutyric acid, malic acid, citric acid, tartaric acid, aminoacetic acid, 2- The resin composition according to claim 3, which is at least one selected from the group consisting of amino-propionic acid, 3-aminopropionic acid, 2-amino-butyric acid, glutamic acid, L-alanine and β-alanine.   The antioxidant (E) is further blended in an amount of 0.01 to 3 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin (A) and the polyacetal resin (B). The resin composition as described.   A molded article comprising the resin composition according to any one of claims 1 to 5.