JP5398106B2 - Resin composition and molded article comprising the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a resin composition and a molded article comprising the same, and more particularly to a resin composition containing a polylactic acid resin excellent in transparency, heat resistance, fluidity and hydrolysis resistance, and a molded article comprising the same. Is.

  In recent years, biodegradable polymers that are decomposed in the natural environment by the action of microorganisms existing in soil or water have attracted attention from the viewpoint of global environmental conservation, and various biodegradable polymers have been developed. Of these, as a biodegradable polymer that can be melt-molded, for example, a fat comprising an aliphatic dicarboxylic acid component such as polyhydroxybutyrate, polycaprolactone, succinic acid or adipic acid, and a glycol component such as ethylene glycol or butanediol. Family polyesters and polylactic acid resins are well known. Among these, polylactic acid resin can be produced at low cost by fermentation using microorganisms, using lactic acid as a raw material for lactic acid as a raw material, and has transparency and a melting point of about 170. It is expected to be a biopolymer that can be melt-molded at a high temperature.

  However, polylactic acid resin has a glass transition temperature of around 60 ° C., and its thermal deformation and rigidity decrease near this temperature are large. Therefore, when it is used as various molded products, it is easily deformed under normal usage conditions. Therefore, a polylactic acid material having excellent heat resistance has been desired.

  Furthermore, in the case of an injection molded product, it is important to have excellent fluidity in terms of molding processability in the injection molding process, and the polylactic acid material is excellent in all of transparency, heat resistance and fluidity. Was desired.

  Moreover, since polylactic acid resin deteriorates by hydrolysis, it is very difficult to use it for a long time under high temperature and high humidity, and a polylactic acid-based material having excellent hydrolysis resistance has been desired.

  Patent Document 1 describes that a resin composition having excellent heat resistance can be obtained with respect to a resin composition composed of polylactic acid and an acrylate polymer. However, it is completely disclosed that the transparency of polylactic acid is maintained. Also in the examples, although heat resistance is improved, there is no example of transparency and fluidity, and a resin composition excellent in all of transparency, heat resistance, fluidity and hydrolysis resistance is obtained. There is no suggestion of a solution.

  Patent Document 2 describes that a resin composition excellent in hydrolyzability can be obtained with respect to a resin composition comprising an α-hydroxycarboxylic acid polymer containing polylactic acid and poly (meth) acrylate. 3 describes that a resin composition excellent in molding processability can be obtained with respect to a resin composition composed of polylactic acid and an acrylic compound, but none of them discloses heat resistance and fluidity. There is no suggestion of a solution for obtaining a resin composition excellent in all of transparency, heat resistance, fluidity and hydrolysis resistance.

Patent Document 4 describes that a resin composition excellent in both transparency and heat resistance is obtained with respect to a resin composition comprising a polylactic acid polymer and an acrylic polymer. Describes that a biaxially stretched film made of a resin composition excellent in both transparency and heat resistance is obtained with respect to a resin composition made of polylactic acid and poly (meth) acrylate. Describes a resin composition composed of polylactic acid and polymethylmethacrylate, and it is described that a resin composition excellent in both transparency and heat resistance can be obtained. It has been described that the glass transition temperature is improved by mixing polymethylmethacrylate. In addition, all have insufficient heat resistance improvement effects, and further improvements are required, in order to obtain a resin composition excellent in all of transparency, heat resistance, fluidity and hydrolysis resistance. There is no suggestion of a solution.
US Pat. No. 5,300,536 (page 1-2) JP-A-8-59949 (page 1-2) JP 2002-155207 A (page 1-2) JP 2004-269720 A (page 1-2) International Patent Publication No. 2004/87812 (page 1-3) Japanese Patent Laying-Open No. 2005-171204 (page 1-2) Polymer Preprints Japan, 42 (3), 1180 (1993) Polymer, 39 (26), 6891 (1998)

  This invention makes it a subject to provide the resin composition containing the polylactic acid-type resin excellent in transparency, heat resistance, fluidity | liquidity, and hydrolysis resistance, and a molded article consisting thereof.

  The present invention employs the following means in order to solve such problems.

That is, the present invention
(1) (A) 0.01 to 30 parts by weight of a reactive compound is blended with 100 parts by weight of (A) polylactic acid resin 1 to 99 parts by weight and (B) 99 to 1 part by weight of methacrylic resin. A resin composition comprising:
(B) At least one methacrylic resin is a methacrylic resin having a weight average molecular weight of 50,000 to 450,000, a glass transition temperature of 110 ° C. or higher, and a syndiotacticity of 40% or higher,
(C) A resin composition, wherein the reactive compound is a polymer containing a glycidyl group-containing vinyl-based unit, and an epoxy value is 1 to 4.5 meq / g,
(2) The resin composition according to (1), wherein the (C) reactive compound is a polymer having a weight average molecular weight of 1,000 to 300,000.
(3) (B) The resin composition according to any one of (1) to (2) , wherein the methacrylic resin includes two or more methacrylic resins that satisfy at least one of the following conditions:
(A) Difference in glass transition temperature is 10 ° C. or more (b) Difference in syndiotacticity is 3% or more (4) Furthermore, (D) inorganic particles are added to a total of 100 parts by weight of resin (A) and resin (B). On the other hand, it is a resin composition formed by blending 0.1 to 50 parts by weight, and (D) the short axis length of the inorganic particles in the resin composition is 1 to 300 nm, and the long axis length is 1. The resin composition according to any one of (1) to (3) , which is ˜1000 nm,
(5) (D) The resin composition according to (4) , wherein the inorganic particles contain silicon,
(6) The ratio of syndiotacticity and isotacticity of the methacrylic resin in the resin composition (syndiotacticity / isotacticity) is 3.0 to 8.0 (1) to (5) A resin composition according to any one of
(7) A molded article comprising the resin composition according to (1) to (6) .
It is.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition containing the polylactic acid-type resin excellent in transparency, heat resistance, fluidity | liquidity, and hydrolysis resistance, and a molded article consisting thereof can be provided.

  The (A) polylactic acid-based resin used in the present invention is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component, but may contain other copolymerization components other than lactic acid. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutyl Polycarboxylic acids such as phosphonium sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglyco Glycerin, pentaerythritol, bisphenol A, aromatic polyhydric alcohol obtained by addition reaction of bisphenol with ethylene oxide, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid, and glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ Lactones such as -butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone can be used.

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

  In addition, as the (A) polylactic acid-based resin of the present invention, it is preferable to use a polylactic acid stereocomplex in terms of heat resistance and moldability. As a method for forming a polylactic acid stereocomplex, for example, L-form is 90% or more, and in terms of heat resistance, preferably 95%, more preferably 98% or more poly-L-lactic acid, and D-form is 90%. As mentioned above, from the viewpoint of heat resistance, a method of mixing 95%, more preferably 98% or more of poly-D-lactic acid using a technique such as melt kneading or solution mixing can be mentioned. As a method, a method of forming a block copolymer composed of a poly-L-lactic acid segment and a poly-D-lactic acid segment can also be mentioned, and poly-L can be easily formed from a polylactic acid stereocomplex. A method of forming a block copolymer comprising a lactic acid segment and a poly-D-lactic acid segment is preferred. In the present invention, the polylactic acid stereocomplex may be used alone, or the polylactic acid stereocomplex and poly-L-lactic acid or poly-D-lactic acid may be used in combination.

  (A) The molecular weight and molecular weight distribution of the polylactic acid-based resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is preferably 1 from the viewpoint of heat resistance. It should be 10,000 or more, more preferably 40,000 or more, still more preferably 80,000 or more, particularly preferably 100,000 or more, and most preferably 130,000 or more. The upper limit is not particularly limited, but in terms of fluidity, it is preferably 500,000 or less, more preferably 300,000 or less, more preferably 250,000 or less, and further preferably 200,000 or less. The weight average molecular weight herein is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  (A) Although it does not specifically limit about melting | fusing point of polylactic acid-type resin, It is preferable that it is 120 degreeC or more, and it is more preferable that it is 150 degreeC or more. The melting point here is the temperature at the peak top of the endothermic peak measured by a differential scanning calorimeter (DSC).

  (A) As a manufacturing method of polylactic acid-type resin, a well-known polymerization method can be used, the direct polymerization method from lactic acid, the ring-opening polymerization method via a lactide, etc. can be used.

  The (B) methacrylic resin used in the present invention is only required to contain a methyl methacrylate component unit as a main component, preferably 60% or more, more preferably 80% or more, and other vinyl monomer component units. Is preferably 40% or less, more preferably 20% or less. Other vinyl monomer component units include aromatic vinyl units such as α-methyl styrene, o-methyl styrene, p-methyl styrene, o-ethyl styrene, p-ethyl styrene, pt-butyl styrene. Monomer, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic anhydride, maleic acid mono N-substituted maleimides such as ethyl ester, itaconic acid, itaconic anhydride, glutaric anhydride, phthalic acid, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylami , Butoxymethylacrylamide, N-propylmethacrylamide, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, aminoethyl acrylate, propylaminoethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 2-hydroxypropyl, glycidyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, butanediol diacrylate, nonanediol diacrylate, polyethylene glycol diacrylate, methyl 2- (hydroxymethyl) acrylate, 2 -(Hydroxymethyl) ethyl acrylate, 2- (hydroxymethyl) butyl acrylate, methacrylic acid, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate Dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, dicyclopentenyloxy methacrylate Ethyl, dicyclopentanyl methacrylate, pentamethylpiperidyl methacrylate, tetramethylpiperidyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, N-vinyldiethylamine, N- Acetyl vinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl Kisazorin, 2-vinyl - oxazoline, 2-acryloyl - oxazoline and 2-styryl - oxazoline and the like, these vinyl monomers may be used alone or in combination. In addition, in terms of heat resistance, low hygroscopicity, and surface hardness, the polymethyl methacrylate copolymer is mainly composed of a ring structural unit such as maleic anhydride, glutaric anhydride, lactone ring, maleimide ring, etc. In the case where a copolymer containing a ring structure in the main chain is used, a resin composition having excellent transparency, heat resistance and fluidity can be obtained. It is more preferable to use a methacrylic resin that does not contain styrene, for example, polymethyl methacrylate.

  In the present invention, (B) at least one methacrylic resin is preferably a methacrylic resin having a weight average molecular weight of 50,000 to 450,000, and is 70,000 to 200,000 in terms of heat resistance and fluidity. More preferably, it is more preferably 9 to 150,000. The weight average molecular weight here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by GPC using hexafluoroisopropanol as a solvent.

  In the present invention, (B) at least one methacrylic resin is preferably a methacrylic resin having a glass transition temperature of 90 ° C. or higher, more preferably 100 ° C. or higher in terms of heat resistance, and 110 More preferably, the temperature is at least 120 ° C, particularly preferably at least 120 ° C. Although an upper limit is not specifically limited, It is preferable that it is 200 degrees C or less at the point of fluidity | liquidity. The glass transition temperature here is a value measured according to the method described in JIS K7121, and is a midpoint glass transition temperature when the temperature is raised at 20 ° C./min by DSC measurement.

  In the present invention, at least one of (B) methacrylic resin is preferably a methacrylic resin having a syndiotacticity of 35%, more preferably 40% or more in terms of heat resistance, % Or more, more preferably 60% or more, and preferably 90% or less, and more preferably 80% or less in terms of fluidity. Further, the heterotacticity of the (B) methacrylic resin is preferably 45% or less, more preferably 40% or less in terms of heat resistance, and 20% or more in terms of fluidity. It is preferable that it is 30% or more. The isotacticity of the (B) methacrylic resin is preferably 20% or less, more preferably 15% or less in terms of heat resistance, and 5% or more in terms of fluidity. It is preferably 8% or more, more preferably 10% or more. Syndiotacticity, heterotacticity, and isotacticity mentioned here are observed as syndiotacticity, heterotacticity, and isotacticity, respectively, in 1H-NMR measurement using deuterated chloroform as a solvent. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, with the total integrated intensity of the peaks of the straight chain branched methyl groups of 0.9 ppm, 1.0 ppm, and 1.2 ppm being 100%. .

  As (B) methacrylic resin used in the present invention, at least one of (B) methacrylic resin has a weight average molecular weight of 50,000 to 450,000, a glass transition temperature of 110 ° C. or higher, and a syndiotacticity of 40% or higher. When a methacrylic resin is used, a resin composition having particularly excellent heat resistance can be obtained, which is preferable.

The (B) methacrylic resin used in the present invention preferably contains two or more methacrylic resins satisfying at least one of the following conditions in terms of heat resistance and fluidity.
(A) Difference in glass transition temperature is 10 ° C. or more (b) Difference in syndiotacticity is 3% or more

  By using a methacrylic resin that satisfies these conditions, the intermolecular interaction with the polylactic acid resin is increased and the affinity is improved, so the effect of improving heat resistance is increased, and transparency, heat resistance and fluidity are increased. An excellent resin composition can be obtained.

  In the present invention, in terms of heat resistance and fluidity, the difference in glass transition temperature is preferably 15 ° C. or higher, and more preferably 20 ° C. or higher. If the difference in glass transition temperature is less than 10 ° C., the effect of improving heat resistance is insufficient. Moreover, although the upper limit of the difference of glass transition temperature is not specifically limited, It is preferable that it is 60 degrees C or less at the point of transparency. The glass transition temperature here is a value measured according to the method described in JIS K7121, and is a midpoint glass transition temperature when the temperature is raised at 20 ° C./min by DSC measurement.

  In the present invention, in terms of heat resistance and fluidity, the difference in syndiotacticity is preferably 5% or more, more preferably 7% or more, and further preferably 10% or more. If the difference in syndiotacticity is less than 3%, the heat resistance improving effect is insufficient. Moreover, the upper limit of the difference of syndiotacticity is not particularly limited, but is preferably 50% or less from the viewpoint of transparency. Syndiotacticity as used herein refers to 0.9 ppm and 1.0 ppm observed as syndiotacticity, heterotacticity and isotacticity, respectively, in 1H-NMR measurement using deuterated chloroform as a solvent. The total integral intensity of 1.2 ppm linear branched methyl group peaks is taken as 100%, and the ratio of the integral intensity of each peak can be calculated as a percentage.

  At least one of the methacrylic resins (B) used in the present invention has a melt flow rate (MFR) of 0.1 to 40 g / 10 min at a temperature of 230 ° C. and a load of 37.2 N in terms of fluidity. It is preferably a methacrylic resin, more preferably 1 to 30 g / 10 min, and further preferably 2 to 20 g / 10 min. Use of the (B) methacrylic resin having an MFR of 0.1 g / 10 min or more is preferable because the fluidity of the resin composition can be maintained and a resin composition having excellent moldability can be obtained. . Moreover, it is preferable to use the methacrylic resin (B) having an MFR of 40 g / 10 min or less since the heat resistance of the resin composition is not impaired.

  As the production method of the (B) methacrylic resin used in the present invention, known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. Although the temperature conditions at the time of superposition | polymerization are not specifically limited, 100 degreeC or less is preferable, 70 degreeC or less is more preferable, 30 degreeC or less is more preferable, and -10 degreeC or less is especially preferable at the heat resistant point of methacrylic resin.

In the present invention, (A) blending ratio of polylactic acid resin and (B methacrylic resin, in terms of heat resistance and flowability, the weight ratio ((A) polylactic acid resin / (B) methacrylic resin) 99 / 1-1 / 99 der is, it more preferably from 90 / 10-10 / 90, more preferably 80 / 20-20 / 80, 70 / 30-30 / 70 Particularly preferred is 59/41 to 35/65.

  When the (B) methacrylic resin used in the present invention contains two or more methacrylic resins, the composition of the two or more methacrylic resins is not particularly limited, but is a glass transition in terms of heat resistance and fluidity. Methacrylic resin 1 having the highest temperature or syndiotacticity as methacrylic resin 1 and methacrylic resin having the lowest glass transition temperature or syndiotacticity as methacrylic resin 2 The weight ratio of methacrylic resin 2 (methacrylic resin 1 / methacrylic resin 2) is preferably 10/90 to 90/10, and more preferably 60/40 to 40/60.

  In the present invention, the reactive compound (C) is a polymer containing a glycidyl group-containing vinyl unit in that a resin composition excellent in transparency, heat resistance, hydrolysis resistance and impact resistance can be obtained. It is preferably a polymer having a weight average molecular weight of 1,000 to 300,000, and particularly preferably a polymer containing a glycidyl group-containing vinyl-based unit. By using a polymer having a weight average molecular weight of 1,000 to 300,000 and containing a glycidyl group-containing vinyl-based unit, the compatibility between the polylactic acid-based resin and the methacrylic resin is improved, and the polylactic acid-based resin and the methacrylic-based resin are improved. As a result, the resin composition having particularly excellent transparency and heat resistance can be obtained.

  In the present invention, specific examples of the raw material monomer for forming the glycidyl group-containing vinyl unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate, maleic acid, itaconic acid Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acid such as, unsaturated glycidyl ether such as allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-4-glycidyl ether, and the like. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit preferably contains a vinyl-based unit other than the glycidyl group-containing vinyl-based unit as a copolymerization component. Depending on the selection, the melting point of the polymer, the glass transition temperature, etc. Can be adjusted. As vinyl units other than glycidyl group-containing vinyl units, acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic anhydride units, unsaturated dicarboxylic acid units, aliphatic types Examples thereof include vinyl units, maleimide units, and other vinyl units. In the present invention, an acrylic vinyl unit is preferably included from the viewpoint of heat resistance. By using a polymer containing an acrylic vinyl unit and a glycidyl group-containing vinyl unit, the compatibility between the polylactic acid resin and the methacrylic resin is improved, so that not only can the heat resistance be improved efficiently, A resin composition having excellent strength and hydrolysis resistance can be obtained.

  Specific examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , Isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Roxypropyl, hydroxypropyl methacrylate, acrylic acid ester or methacrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, Acrylic vinyl units having an amino group such as acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. In particular, in terms of heat resistance and hydrolysis resistance, acrylic acid and methacrylic acid are used. , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate T-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile are preferred, and acrylic acid and methacrylic acid are also preferred. , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, methacrylate 2-ethylhexyl, acrylonitrile, methacrylonitrile are preferable in terms of heat resistance, methyl methacrylate is more preferable. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer that forms the vinyl carboxylate unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Monofunctional aliphatic vinyl carboxylates such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate and vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl cinnamate, etc. And polyfunctional vinyl carboxylates such as vinyl aromatic carboxylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonic acid and vinyl sorbate. Among them, vinyl acetate is preferably used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer for forming the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, 4 -Dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned, among which styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  Examples of the raw material monomer that forms the unsaturated dicarboxylic acid anhydride unit include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, or aconitic acid anhydride, among which maleic acid anhydride is preferably used. The These may be used alone or in combination of two or more.

  Examples of the raw material monomer for forming the unsaturated dicarboxylic acid-based unit include maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid and the like. Among these, maleic acid and itaconic acid are preferably used. These may be used alone or in combination of two or more.

  Examples of raw material monomers for forming aliphatic vinyl units include ethylene, propylene, and butadiene. Examples of raw material monomers for forming maleimide units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- As other raw material monomers for forming vinyl units such as isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide, N-vinyldiethylamine, N- Acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene and the like can be mentioned, and these can be used alone or in combination of two or more.

In the present invention, the polymer containing a glycidyl group-containing vinyl unit may have an epoxy value in the range of 1 to 4.5 meq / g in that a resin composition having excellent heat resistance can be obtained. The range is preferably 2 to 4.5 meq / g, and more preferably 2.5 to 4 meq / g. Use of an epoxy with an epoxy value of 1 meq / g or more provides a sufficient effect of improving melt viscosity characteristics. Use of an epoxy with an epoxy value of 4.5 meq / g or less lowers moldability due to gelation or the like. This is preferable because it does not occur. Here, the epoxy value is a value measured by a hydrochloric acid-dioxane method. In addition, the epoxy value of the polymer containing a glycidyl group-containing vinyl-based unit can be adjusted by adjusting the content of the glycidyl group-containing vinyl-based unit.

  In the present invention, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited, but is preferably in the range of 30 to 100 ° C. in terms of excellent handling properties. More preferably, it is in the range of ˜70 ° C., most preferably in the range of 50 to 65 ° C. The glass transition temperature here is a value measured by DSC according to the method described in JIS K7121, and is the midpoint glass transition temperature when the temperature is raised at 20 ° C./min.

  In addition, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit can be controlled by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit usually contains a volatile component because unreacted raw material monomers and solvents remain. The amount of the non-volatile component that is the balance is not particularly limited, but it is preferable that the non-volatile component amount is large from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by weight or more, more preferably 97% by weight or more, further preferably 98% by weight or more, and most preferably 98.5% by weight or more. preferable. In addition, the non-volatile component here represents the remaining amount ratio when the sample 10g is heated at 110 degreeC for 1 hour in nitrogen atmosphere.

  In the present invention, a polymer containing a glycidyl group-containing vinyl-based unit may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. Contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, the method for producing a polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. When these methods are used, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used, but these remain as impurities in a polymer containing a vinyl unit containing a glycidyl group finally obtained. There are things to do. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, particularly 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  As a method for producing a polymer containing a glycidyl group-containing vinyl-based unit that satisfies the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, and the like as described above, a high temperature of 150 ° C. or higher is applied. A method of continuous bulk polymerization under a pressure condition (preferably 1 MPa or more) in a short time (preferably 5 to 30 minutes) is a high polymerization rate, a polymerization initiator or a chain transfer agent that causes impurities and sulfur content And more preferable in that no solvent is used.

  In the present invention, the compounding amount of the (C) reactive compound is preferably 0.01 to 30 parts by weight with respect to a total of 100 parts by weight of the (A) polylactic acid resin and (B) methacrylic resin, 0.05 -20 parts by weight is more preferable, 0.1-10 parts by weight is further preferable, and 0.5-3 parts by weight is particularly preferable. (C) If the compounding amount of the reactive compound is less than 0.01 parts by weight, the effect of improving the heat resistance and hydrolysis resistance of the resin composition tends to be insufficient, and if it exceeds 30 parts by weight, the gel There is a risk that fluidity will be reduced due to the change of the flow rate.

  In the present invention, it is preferable to further mix (D) inorganic particles from the viewpoint of heat resistance, the short axis length of the inorganic particles in the resin composition is 1 to 300 nm, and the long axis length is 1. It is preferable that it is -1000 nm. In terms of transparency, the length of the short axis of the inorganic particles (D) is more preferably 5 to 200 nm, further preferably 10 to 100 nm, and the length of the long axis is 10 to 900 nm. More preferably, it is more preferably 50 to 800 nm. In the present invention, the short axis length and the long axis length of the inorganic particles are obtained by observing the resin composition at 20,000 times using an electron microscope, and about 20 arbitrary inorganic particles, preferably 100 particles. The shape is observed and measured, and the shortest length is taken as the minor axis direction, the longest length is taken as the major axis direction, and each is an average value.

  In the present invention, the inorganic particles (D) may be granular, spherical, plate-like, or fibrous, but are preferably plate-like from the viewpoint of heat resistance.

  In the present invention, the granular or spherical inorganic particles include zinc oxide, magnesium oxide, iron oxide, titanium oxide, titania, zirconia, ceria, alumina, silica, calcium carbonate, talc, mica, kaolin, graphite powder, carbon black, etc. Among them, silica is preferable.

  In the present invention, as the plate-like inorganic particles, silicates such as talc, mica, glass flakes, montmorillonite and smectite can be used, and among them, silicates are preferable.

  In the present invention, glass fiber, carbon fiber, zinc oxide, alumina, calcium titanate, potassium titanate, barium titanate, aluminum borate, magnesium borate, magnesium oxysulfate fiber, etc. are used as the fibrous inorganic particles. be able to.

  In the present invention, the inorganic particles (D) are more preferably those containing silicon, and specific examples thereof include silica and silicate. Among them, layered silicate is more preferable, and organic modification More preferably, it is a layered silicate. In the present invention, by performing elemental analysis using an electron microscope-energy dispersive X-ray analyzer (EDX), it can be determined that the particles are inorganic particles, and silicon can be detected. .

  In the present invention, the silica may be powder, water or an organic solvent dispersed sol (colloidal silica), but colloidal silica is preferable in terms of transparency. Furthermore, in terms of transparency, the surface is treated with at least one functional group selected from a hydroxyl group, amino group, amide group, carboxyl group, glycidyl group, acid anhydride group, carbodiimide group, and oxazoline group. Is preferred. By using the surface-treated silica, the affinity with the matrix resin is improved, which is effective in suppressing aggregation and dispersibility of inorganic particles, and can be uniformly dispersed in the resin composition. A resin composition having excellent transparency can be obtained.

  In the present invention, the organically modified layered silicate is a layered silicate in which an exchangeable cation or anion existing between layers is exchanged with an organic onium ion or an organic anion, and in particular, the exchangeable cation is an organic onium ion. Exchanged layered silicates are preferred.

  A layered silicate having exchangeable ions between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 Å are laminated, and exchangeable ions are provided between the layers of the plate-like materials. have. The ion exchange capacity is 0.2 to 3 meq / g, and preferably the ion exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li type Fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, swellable mica such as Li-type tetrasilicon fluorine mica, hydrotalcite, etc., which may be natural or synthesized good. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.

  Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  The quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium. Alkyltrimethylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldialkylammonium ions such as dimethyldioctadecylammonium, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, benzene Such as benzethonium ion having two thereof.

  In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group.

  Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more.

  Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  Examples of the organic anion include a long-chain carboxylic acid, and examples thereof include lauric acid, decanoic acid, stearic acid, dodecadicarboxylic acid, and dimer acid.

  In the present invention, the organically modified layered silicate can be produced by reacting a layered silicate having an exchangeable cation or anion between layers, an organic onium ion or an organic anion by a known method. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a liquid or molten organic salt with a layered silicate can be used.

  In the present invention, the amount of organic ions relative to the layered silicate is the cation exchange capacity of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. In general, it is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents.

  In addition, it is preferable to use the organically modified layered silicate after pretreatment with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the organically modified layered silicate is preferably uniformly dispersed in the resin composition. Here, uniform dispersion means that the layered silicate is dispersed in a laminated state of 5 layers or less without having a local mass.

  In the present invention, the blending amount of (D) inorganic particles is preferably 0.1 to 50 parts by weight with respect to a total of 100 parts by weight of (A) polylactic acid resin and (B) methacrylic resin, 0.5 -20 parts by weight is more preferable, and 1-10 parts by weight is particularly preferable.

  In the resin composition of the present invention, fillers (glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers, etc.), stabilizers (antioxidants, ultraviolet absorbers, etc.) are within the range not impairing the object of the present invention. ), Lubricants, mold release agents, flame retardants, colorants including dyes and pigments, crystal nucleating agents, plasticizers, antistatic agents, and the like. Especially, it is preferable to mix | blend a mold release agent at the point that the resin composition excellent in mechanical characteristics, a moldability, heat resistance, transparency, etc. is obtained. As the mold release agent, those usually used for mold release agents for thermoplastic resins can be used. Specifically, fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, partially aliphatic saponified esters, paraffin, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohols Examples thereof include esters, fatty acid polyglycol esters, and modified silicones. The compounding amount of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight as a total of (A) polylactic acid resin and (B) methacrylic resin. preferable.

  Further, for the resin composition of the present invention, other thermoplastic resins (for example, polyethylene resin, polypropylene resin, polymethylpentene resin, cyclic olefin resin, acrylonitrile, butanediene, Styrene (ABS) resin, acrylonitrile / styrene (AS) resin, cellulose resin such as cellulose acetate, polyamide resin, polyacetal resin, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyphenylene oxide resin, polyarylate Resins, polysulfone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, polyetherimide resins, etc.) and thermosetting resins (eg phenol Le resins, melamine resins, polyester resins, silicone resins, and epoxy resins) may be further added at least one or more kinds of such.

  Although the manufacturing method of the resin composition of this invention is not specifically limited, For example, (A) polylactic acid-type resin, (B) methacrylic-type resin, (C) reactive compound, and other as needed After blending the additives in advance, a method of uniformly melting and kneading with a single screw or twin screw extruder above the melting point, a method of removing the solvent after mixing in the solution, etc. are used. A method of uniformly melt-kneading with a twin-screw extruder is preferred, and a method of uniformly melt-kneading with a twin-screw extruder is more preferred in that a resin composition excellent in transparency, heat resistance and fluidity can be obtained.

  Regarding the resin composition of the present invention, the ratio of syndiotacticity and isotacticity of the methacrylic resin in the resin composition (syndiotacticity / isotacticity) is 2.5 to 8.0. preferable. Further, from the viewpoint of heat resistance and fluidity, it is more preferably 3.0 to 8.0, further preferably 3.0 to 5.5, and 3.0 to 5.0. Particularly preferred. Syndiotacticity, heterotacticity, and isotacticity mentioned here are observed as syndiotacticity, heterotacticity, and isotacticity, respectively, in 1H-NMR measurement using deuterated chloroform as a solvent. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, with the total integrated intensity of the peaks of the straight chain branched methyl groups of 0.9 ppm, 1.0 ppm, and 1.2 ppm being 100%. .

  About the resin composition of this invention, it is preferable that a glass transition temperature is 70 degreeC or more at a heat resistant point, It is more preferable that it is 75 degreeC or more, It is further more preferable that it is 80 degreeC or more, 90 degreeC The above is particularly preferable. Although an upper limit is not specifically limited, From a fluidity | liquidity point, it is preferable that it is 150 degrees C or less, and it is more preferable that it is 120 degrees C or less. The glass transition temperature here is a value measured by DSC according to the method described in JIS K7121, and is the higher of the midpoint glass transition temperature or the extrapolation transition end temperature. In DSC measurement, the DSC curve is bent due to the change in specific heat capacity, and the glass transition temperature region can be detected by the shape in which the base line moves in parallel. The midpoint glass transition temperature refers to the tangent lines of the respective base lines below the bending point and above the bending point so as to be parallel to each other, and at each position where the specific heat capacity change is halved. This is the intersection of a DSC curve that draws a straight line parallel to the baseline and bends. The extrapolation transition end temperature refers to the intersection of the tangent line of the base line of the temperature above the bending point and the tangent line of the point having the maximum inclination at the bent part.

  With respect to the resin composition of the present invention, in terms of heat resistance, the deflection temperature under load (DTUL) measured at a load of 0.45 MPa according to ASTM D648 is preferably 60 ° C. or higher, and preferably 70 ° C. or higher. More preferably, it is more preferably 80 ° C. or higher.

  The resin composition of the present invention is preferably transparent. Here, 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. Specifically, the haze when formed into a molded product having a thickness of 20 μm or more, preferably 1 mm is preferably 30% or less, more preferably 10% or less in terms of excellent transparency. More preferably, the haze is 5% or less. In the present invention, haze is a value measured according to JIS K7105. Further, the transparency can also be determined by the total light transmittance measured according to JIS K6714, the total light transmittance is preferably 80% or more, more preferably 85% or more, More preferably, it is 90% or more.

  For the resin composition of the present invention, the melt flow rate (MFR) is not particularly limited, but in terms of heat resistance, the MFR measured at 190 ° C. and 21.2 N load is 30 g / 10 min or less according to JIS K7210. Preferably, it is 20 g / 10 min or less, and more preferably 15 g / 10 min or less. When MFR exceeds 30 g / 10 min, the heat resistance tends to decrease. In terms of fluidity, it is preferably 0.1 g / 10 minutes or more, more preferably 1 g / 10 minutes or more, and further preferably 3 g / 10 minutes or more. When the MFR is less than 0.1 g / 10 min, the fluidity is lowered and the processability at the time of injection molding tends to be lowered.

  The surface hardness of the resin composition of the present invention is not particularly limited, but the pencil hardness measured according to JIS K-5600 is preferably HB or higher, more preferably F or higher, and H or higher. Further preferred. When the pencil hardness is lower than HB, the surface is easily scratched, which is not preferable. When the resin composition of the present invention is used as an optical recording medium, it is preferably HB or more, and is preferably HB or more, in that it is less likely to be scratched when processed into a substrate and reading errors are less likely to occur. Further, it is preferably 3H or less, more preferably 2H or less, from the viewpoint that the optical recording medium is less likely to be destroyed by an impact such as dropping.

  With respect to the resin composition of the present invention, the saturated water absorption is not particularly limited, but the saturated water absorption measured according to ASTM D570 is preferably 0.4% by weight or less, more preferably 0.3% by weight or less. Preferably, it is more preferably 0.2% by weight or less, and particularly preferably 0.1% by weight or less. The lower limit is not particularly limited. If the saturated water absorption exceeds 0.4% by weight, deformation due to moisture absorption is likely to occur and the possibility of being unusable increases.

  Although the retardation (birefringence amount) of the resin composition of the present invention is not particularly limited, it was measured by irradiating a laser beam of 23 ° C. and 405 nm at an angle of 30 ° C. with respect to the substrate surface using a commercially available ellipsometer. The retardation is preferably 50 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, particularly preferably 10 nm or less, and most preferably 5 nm or less. When the resin composition of the present invention is used as an optical recording medium, if the retardation exceeds 50 nm, reading errors and the like are liable to occur, such being undesirable.

  The resin composition of the present invention can be processed into various molded products and used by a method such as injection molding or extrusion molding.

  Examples of the molded product made of the resin composition of the present invention include injection molded products, extrusion molded products, blow molded products, films and sheets. In the present invention, a molded product having a portion having a thickness of 20 μm or more is preferable and a molded product having a portion having a thickness of 1 mm or more is more preferable in terms of excellent heat resistance. Furthermore, in terms of excellent heat resistance and impact resistance, the molded product preferably has a portion having a thickness of 50 mm or less, more preferably a molded product having a portion of 10 mm or less, and a portion of 5 mm or less. More preferably, it is a molded product.

  The molded product made of the resin composition of the present invention preferably has a portion having a thickness of 20 μm or more, preferably 1 mm and a haze of 30% or less, in terms of excellent transparency. It is more preferable to have a portion that is 10% or less, and even more preferable to have a portion that is 5% or less. In the present invention, haze is a value measured using a haze meter in accordance with JIS K7105.

  The molded article made of the resin composition of the present invention can be used for various applications such as electric / electronic parts, building members, automobile parts, various containers, daily necessities, household goods and sanitary goods.

  Specifically, mobile terminals such as relay cases, coil bobbins, optical pickup chassis, motor cases, notebook computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile phones, mobile personal computers, handheld mobiles Housing and internal components, recording media (CD, DVD, PD, FDD, etc.) drive housing and internal components, copier housing and internal components, facsimile housing and internal components, parabolic antennas and other electrical / electronic components Can be mentioned. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dewatering bag, concrete formwork and other civil engineering related parts, air flow meter, air pump, thermostat housing, engine mount, ignition hobbin , Ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, AB Actuator case, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, Timing belt covers, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes and other automotive underhood parts, torque control levers, safety belt parts, register blades, washer levers, Window regulator handle, knob of window regulator handle, passing light lever, samba Automotive interior parts such as Iser brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Automotive exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors and other automotive connectors, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, fans, Tegs, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection nonwoven fabrics, seedlings Pot, vegetation pile, seed string tape, germination sheet, house lining sheet, farm-bi fastener, slow-release fertilizer, root-proof sheet, garden net, insect net, young tree net, printed laminate, fertilizer bag, sample Agricultural materials such as bags, sandbags, beast harm prevention nets, inducement strings, windproof nets, disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, etc., medical non-woven fabrics (stitching reinforcements, adhesion prevention films, Prosthetic repair materials), wound dressing materials, wound tape bandages, sticky material base fabric, surgical sutures, fracture reinforcements, medical films and other medical supplies, calendars, stationery, clothing, food packaging films, trays , Blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets and other containers, tableware, hot-fill containers, microwave cooking containers cosmetics , Wrap, foam buffer, paper lami, shampoo bottle, beverage bottle, cup, candy packaging, shrink label, lid material, envelope with window, fruit basket, hand tape, easy peel packaging, egg pack, HDD packaging, Compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural fiber composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs Paste, carpet, tablecloth, futon, wallpaper, furoshiki interior goods, carrier tape, print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card , IC card, paper, leather, non-woven Hot melt binders such as cloth, magnetic material, zinc sulfide, powder binders such as electrode materials, optical elements, conductive embossed tape, IC trays, golf tees, garbage bags, plastic bags, various nets, toothbrushes, stationery, draining nets , Body towel, hand towel, tea pack, drainage filter, clear file, coat agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel Useful as kitchen cabinets, pen caps, gas lighters, etc.

  In particular, the resin composition of the present invention includes CD, CD-ROM, CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, laser disc (registered trademark), Blu-ray disc, and the like. It is useful as a substrate for optical recording media.

  In the present invention, the production method of the substrate of the optical recording medium is not particularly limited, and a known method can be used, and examples thereof include an injection molding method, an extrusion molding method, an injection press molding method, and the like. An injection molding method is preferable in that a product having a large amount can be stably produced in large quantities. Various layers such as a reflective layer, a recording layer, an adhesive layer, a dielectric layer, and a protective layer formed on the substrate can be formed using a known method. In addition, as an adhesive agent used for an adhesive layer, it is preferable to use high heat-resistant adhesive agents, such as a polyimide type, from a heat resistant point. In addition, by changing the type of layers formed on the substrate, the number of stacked layers, and the like, a reproduction-only type, a write-once type, a rewritable type, and the like can be manufactured.

  The resin composition of the present invention and a molded product comprising the resin composition can be recycled. For example, the resin composition and a molded product comprising the resin composition are heat-treated at 80 ° C. or higher, preferably 100 ° C. or higher, pulverized, preferably powdered, and then used with a solvent such as acetone or tetrahydrofuran, and (B) methacryl The system resin is isolated, and then the (A) polylactic acid resin can be isolated from the residue using a solvent such as chloroform. The isolated resins can be used alone, and the resin composition obtained by further blending them can be used in the same manner as the resin composition of the present invention, and can also be formed into a molded product.

  Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. Here, the compounding ratio in an Example shows a weight part. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A) Polylactic acid resin (A-1) Poly L lactic acid resin (D-form 1.2%, weight average molecular weight 150,000)

(B) Methacrylic resin (B-1) Methacrylic resin (“SUMIPEX LG21” manufactured by Sumitomo Chemical Co., Ltd.) Weight average molecular weight 80,000, glass transition temperature 105 ° C., syndiotacticity 41%, MFR 21 g / 10 min (230 ° C., 37. 2N))
(B-2) Methacrylic resin (Kuraray “Parapet” HR-L, weight average molecular weight 90,000, glass transition temperature 117 ° C., syndiotacticity 56%, MFR 2 g / 10 min (230 ° C., 37.2 N))
(B-3) Methacrylic resin (“SUMIPEX” LG35, manufactured by Sumitomo Chemical Co., Ltd., weight average molecular weight 100,000, glass transition temperature 90 ° C., syndiotactic 39%, MFR 35 g / 10 min (230 ° C., 37.2 N) )

(C) Reactive compound (C-1) Glycidyl group-containing acrylic / styrene copolymer ("ARUFON" UG4040 manufactured by Toagosei Co., Ltd., weight average molecular weight 10,000, epoxy value 2.1 meq / g)
(C-2) Glycidyl group-containing acrylic / styrene copolymer (“John Crill” ADR-4368 manufactured by Johnson Polymer, weight average molecular weight 8,000, epoxy value 3.5 meq / g)
(C-3) Glycidyl group-containing acrylic copolymer ("Marproof" G2050M manufactured by NOF Corporation, weight average molecular weight 210,000, epoxy value 2.9 meq / g )

(D) Inorganic particles (D-1) Montmorillonite (organic modified layered silicate) exchanged with 12-aminododecanoic acid hydrochloride obtained in Reference Example 2

[Reference Example 1] (B-4) Production example of methacrylic resin containing glutaric anhydride unit 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide, 0.3 part by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water The reactor was charged and maintained at 70 ° C. while replacing the reactor with nitrogen gas. The reaction was continued until the monomer was completely converted into a polymer to obtain an aqueous solution of methyl methacrylate / acrylamide copolymer. The resulting aqueous solution was used as a suspending agent. A solution prepared by dissolving 0.05 parts by weight of the above-mentioned methyl methacrylate / acrylamide copolymer suspension in 165 parts by weight of ion-exchanged water in a stainless steel autoclave having a volume of 5 liters and equipped with a baffle and a foudra-type stirring blade. The mixture was supplied and stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was set as the start of polymerization, and kept for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a bead-shaped copolymer (b-4). The polymerization rate of this copolymer (b-4) was 98%.
Methacrylic acid: 28 parts by weight Methyl methacrylate: 72 parts by weight n-dodecyl mercaptan: 0.8 parts by weight Lauryl peroxide: 0.4 parts by weight

  Next, using the obtained (b-4), HTM 38 mm (biaxial portion L / D = 34, biaxial / uniaxial composite continuous kneading and extruding device of non-meshing different direction rotation equipped with a flow rate adjusting valve. Using a uniaxial part L / D = 14, manufactured by CTE), 0.2 part of lithium acetate was added, and an intramolecular cyclization reaction was performed at a raw material supply rate of 10 kg / h, a screw rotation speed: 40 rpm, and a cylinder temperature of 285 ° C. And pellet-shaped glutaric anhydride unit-containing acrylic resin (B-4) was obtained. The reaction was performed while purging nitrogen from the hopper at a rate of 10 L / min.

It was 137 degreeC as a result of measuring the glass transition temperature (Tg) by DSC about the obtained acrylic resin (B-4) containing glutaric anhydride unit. Subsequently, 1H-NMR measurement was carried out using dimethyl sulfoxide heavy solvent, and spectral assignment was made at 0.5 to 1.5 ppm peak for α-methyl group of methacrylic acid, methyl methacrylate and glutaric anhydride ring compounds. The peak of 1.6 to 2.1 ppm is the hydrogen of the methylene group of the polymer main chain, the peak of 3.0 ppm is the hydrogen of methyl methacrylate (-COOCH3), the peak of 11.9 ppm is the methacrylic acid As a result of calculating the composition of each copolymer unit from the integral ratio of the spectrum as hydrogen of the carboxylic acid, it was as follows.
Methacrylic acid unit: 3% by weight
Methyl methacrylate unit: 64% by weight
Glutaric anhydride unit: 33% by weight

[Reference Example 2] Production Example of (D-1) 100 g of Na-type montmorillonite (Kunimine Industries: “Kunipia F”, cation exchange capacity 120 meq / 100 g) was stirred and dispersed in 10 liters of warm water, and 12-aminododecane was added thereto. 2 L of warm water in which 30.2 g of hydrochloride (equivalent to the cation exchange capacity) was dissolved was added and stirred for 1 hour, and the resulting precipitate was filtered and washed with warm water three times. E-1 was obtained by vacuum drying at ° C.

  The measurement method and determination method used in the present invention are shown below. In addition, when there was no designation | designated about the shape of a molded article, it evaluated using the pellet-shaped resin composition.

(1) Weight average molecular weight (Mw)
It is a value of weight average molecular weight in terms of standard PMMA measured by gel permeation chromatography (GPC). Hexafluoroisopropanol was used as a solvent, the flow rate was 0.5 mL / min, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected and measured.

(2) Syndiotacticity and isotacticity These are values measured by 1H-NMR measurement. 1H-NMR measurement was performed using JNM-AL400 manufactured by JEOL Ltd., using deuterated chloroform as a solvent, and a sample concentration of 20 mg / mL. Each peak is defined as the total integrated intensity of the straight-chain branched methyl groups of 0.9 ppm, 1.0 ppm, and 1.2 ppm observed as syndiotacticity, heterotacticity, and isotacticity, respectively. The values representing the percentage of the integrated intensity of each as a percentage were defined as syndiotacticity, heterotacticity, and isotacticity, respectively.

(3) Glass transition temperature (Tg)
According to JIS K7121, a differential scanning calorimeter (Seiko Electronics RDC220) was used for measurement. The measurement conditions are a sample 10 mg, a nitrogen atmosphere, and a temperature increase rate of 20 ° C./min.

(4) Heat resistance (DTUL)
According to ASTM D648, the deflection temperature under load (load 0.45 MPa) of a molded article of 12.7 mm × 127 mm × 3 mm was measured.

(5) Transparency Using a Nippon Denshoku Industries haze meter NDH-300A, the haze of a 5 cm × 5 cm × 1 mm plate-shaped molded product was measured according to JIS-K7105.

(6) Fluidity (MFR)
About the fluidity | liquidity of the resin composition, it measured in 190 degreeC and a 21.2N load according to JISK7210.

(7) Impact Characteristics According to ASTM D256, the Izod impact strength of a strip-shaped product with a 3 mm thickness notch was measured.

(8) Tensile strength According to ASTM method D638, an ASTM No. 1 dumbbell molded product was used to conduct a tensile test.

(9) Hydrolysis resistance After the ASTM No. 1 dumbbell molded product was treated in a thermostatic chamber at 60 ° C. and 95% relative humidity for 500 hours, the tensile strength was measured to determine the tensile strength retention. It can be said that the greater the tensile strength retention, the better the hydrolysis resistance.

(10) (D) Dispersion state of inorganic particles in resin composition Observation using a transmission electron microscope (TEM) -energy dispersive X-ray analyzer (EDX) at a magnification of 20,000, and silicon-containing particles by EDX For any 20 particles that could be determined, the length of the short axis and the length of the long axis were measured, and the average value was obtained.

[Examples 2 to 6 , Comparative Examples 1 to 5 , 10, 11 ]
As shown in Table 1, a polylactic acid resin, a methacrylic resin, and a reactive compound are blended, and melt-kneaded using a 30 mm diameter twin screw extruder under conditions of a cylinder temperature of 200 ° C. and a rotation speed of 200 rpm. A resin composition was obtained.

  The obtained resin composition was injection-molded at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C. using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries, and a molded product of 12.7 mm × 127 mm × 3 mm, 5 cm × 5 cm × 1 mm Plate-shaped molded product, 3 mm thick notched strip-shaped molded product, and ASTM No. 1 dumbbell molded product.

  Table 1 shows the results of various evaluations using the obtained molded product.

  From the results in Table 1, the following is clear.

From the comparison with Examples 2 to 6 and Comparative Examples 1 to 5 , 10 and 11 , the resin composition formed by blending a polylactic acid resin, a methacrylic resin and a reactive compound has heat resistance, transparency and fluidity. It can be seen that it is excellent in impact resistance, strength, and hydrolysis resistance. In addition, Examples 1 and 3 indicate that the methacrylic resin is particularly excellent in heat resistance, strength, and hydrolysis resistance when the glass transition temperature is 110 ° C. or higher .

[ Examples 14 to 15 and Comparative Example 7]
As shown in Table 3, a resin composition and a molded product were obtained in the same manner as in Example 1 except that a polylactic acid resin, a methacrylic resin, and a reactive compound were blended. Table 3 shows the results of various evaluations.

  From the results in Table 3, the following is clear.

From the comparison between Examples 14 to 15 and Comparative Example 7, the resin composition formed by blending a polylactic acid resin, a methacrylic resin and a reactive compound was found to have heat resistance, transparency, fluidity, impact resistance, strength and It turns out that it is excellent in hydrolysis resistance. As a methacrylic resin, a resin composition formed by blending two methacrylic resins satisfying any one or more conditions of a glass transition temperature difference of 10 ° C. or more or a syndiotactic difference of 3% or more. It can be seen that the product is excellent in heat resistance, transparency, fluidity, impact resistance, strength, and hydrolysis resistance .
[Examples 18 to 19, Comparative Examples 8 to 9]
As shown in Table 4, a resin composition and a molded product were obtained in the same manner as in Example 1 except that a polylactic acid resin, a methacrylic resin, a reactive compound, and inorganic particles were blended. Table 4 shows the results of various evaluations.

  From the results in Table 4, the following is clear.

  From a comparison between Examples 18-19 and Comparative Examples 8-9, a resin composition comprising a polylactic acid resin, a methacrylic resin, a reactive compound, and inorganic particles containing silicon having a particle diameter of 5 to 500 nm, It turns out that it is excellent in heat resistance, transparency, fluidity | liquidity, impact resistance, and hydrolysis resistance.

Claims (7)

(C) Reactive compound 0.01-30 weight part is mix | blended with respect to a total of 100 weight part of (A) polylactic acid-type resin 1-99 weight part and (B) methacryl-type resin 99-1 weight part. A resin composition comprising:
(B) At least one methacrylic resin is a methacrylic resin having a weight average molecular weight of 50,000 to 450,000, a glass transition temperature of 110 ° C. or higher, and a syndiotacticity of 40% or higher,
(C) A resin composition, wherein the reactive compound is a polymer containing a glycidyl group-containing vinyl-based unit and has an epoxy value of 1 to 4.5 meq / g. The resin composition according to claim 1, wherein the reactive compound (C) is a polymer having a weight average molecular weight of 1,000 to 300,000. (B) methacrylic resins, resin composition according to any one of claims 1-2 comprising two or more methacrylic resins satisfying at least one of the following conditions.
(A) Difference in glass transition temperature is 10 ° C. or more (b) Difference in syndiotacticity is 3% or more Furthermore, (D) a resin composition comprising 0.1 to 50 parts by weight of inorganic particles based on a total of 100 parts by weight of resin (A) and resin (B), wherein (D) in the resin composition The resin composition according to any one of claims 1 to 3 , wherein the inorganic particles have a minor axis length of 1 to 300 nm and a major axis length of 1 to 1000 nm. (D) The resin composition according to claim 4 , wherein the inorganic particles contain silicon. The ratio of the methacrylic resin of syndiotacticity and isotacticity in the resin composition (syndiotacticity / isotacticity) of any one of claims 1 to 5, which is 3.0 to 8.0 The resin composition described in 1. Molded article comprising a resin composition according to claim 1-6.