JP2006241445A - Thermoplastic resin composition and its molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having good moldability and excellent in appearance and peeling resistance and its thermoplastic resin molded product. <P>SOLUTION: The thermoplastic resin composition comprises (A) 10-90 pts.wt. lactic acid-based resin and (B) 90-10 pts.wt. polypropylene-based resin (with the proviso that total of the components (A) and (B) is 100 pts.wt.) and (C) 1-30 pts.wt. (based on total of components A and B) aromatic vinyl-conjugated diene block copolymer modified with a polar functional group. The molded product is composed of a thermoplastic resin composition having good moldability and excellent in appearance and peeling resistance. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition comprising a lactic acid resin and a polypropylene resin and an aromatic vinyl / conjugated diene block copolymer modified with a polar functional group compatible therewith, and a molded article comprising the same. . More specifically, the present invention relates to a molded article made of a thermoplastic resin composition having good moldability, excellent appearance, and excellent peel resistance.

  As awareness of global environmental issues increases, fossil raw materials, petroleum resources are depleted, and carbon dioxide is increasing. Polylactic acid having excellent moldability has attracted attention as a plant-derived resin that uses lactic acid obtained by fermentation from cereal resources such as corn as a raw material. However, although polylactic acid is a crystalline resin, its crystallization rate is remarkably slow, and although the melting point of crystalline polylactic acid is as high as 160-180 ° C, the heat resistance of amorphous polylactic acid is low because of its glass transition point of 58 ° C. The heat deformation temperature is as low as less than 60 ° C., and the Izod impact strength is inferior and weak at 30 J / m, which limits the application development. Improvement of these lactic acid-based resins is desired for use in everyday environments.

As an example of a system in which polyolefin is mixed with polylactic acid in order to improve the strength, Japanese Patent Application Laid-Open No. 2000-327847 shows an example in which the mechanical strength is improved. The properties are extremely low. Simply blending and kneading the two results in phase separation and incompatibility. The polylactic acid has a large dispersed particle size of 10 μm or more, has a poor appearance, and causes delamination on the surface of the molded product. Is difficult (Patent Document 1).
JP 2000-327847 A

  The problem to be solved by the present invention is that lactic acid-based resins and polypropylene-based resins and aromatic vinyl / conjugated diene block copolymers modified with polar functional groups having high compatibility with them are used as constituent components, and moldability is improved. It is to obtain a thermoplastic resin composition having a good appearance and excellent peel resistance and a molded product thereof without damage.

  The present invention comprises 10 to 90 parts by weight of a lactic acid resin (A), 90 to 10 parts by weight of a polypropylene resin (B) (provided that the total of (A) and (B) is 100 parts by weight) and a polar functional group. 1. A thermoplastic resin composition comprising 1 to 30 parts by weight of the aromatic vinyl / conjugated diene block copolymer (C) modified with 1. is provided.

  The thermoplastic resin composition as described above, wherein the polar functional group of the aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group is a base.

  The aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group was selected from the group consisting of imine-modified SBS (C1), imine-modified SBBS (C2), and imine-modified SEBS (C3). 1 type or 2 types or more of copolymers are included, and the total amount of the copolymer includes 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the lactic acid resin (A) and the polypropylene resin (B). The thermoplastic resin composition described above is a preferred embodiment of the present invention.

The lactic acid resin (A) and the polypropylene resin (B) are resins having a melt viscosity under a shear rate of 1216 sec ⁻¹ at 200 ° C. satisfying the range of the following formula (1). 10 to 90 parts by weight, polypropylene resin (B) 90 to 10 parts by weight (provided that the total of (A) and (B) is 100 parts by weight) and an aromatic vinyl / conjugated diene modified with a polar functional group A thermoplastic resin composition comprising 1 to 30 parts by weight of the block copolymer (C) and having an average dispersed particle size of the lactic acid resin (A) of 1 μm or less is a preferred embodiment of the present invention.

Here, Z (A) is the melt viscosity of the lactic acid resin (A) at 200 ° C. and a shear rate of 1216 sec ⁻¹ , Z (B): 200 ° C. of the polypropylene resin (B), and a shear rate of 1216 sec ^{− 1} is the melt viscosity under ¹ .

A molded body made of the thermoplastic resin composition is also a preferred embodiment of the present invention.
A sheet made of the thermoplastic resin composition is also a preferred form of the present invention.

  Test method for temperature dependency of dynamic viscoelasticity (JIS-K-7198, method A) The storage elastic modulus (E ′) at 100 ° C. is 20 MPa or more and 3000 MPa or less. Is a preferred form.

  According to the present invention, it is possible to obtain a thermoplastic resin composition having a good appearance and excellent peel resistance on the product surface, and a molded product thereof without impairing moldability.

Hereinafter, the present invention will be described in detail.
In the present invention, the sheet means a sheet including both a sheet and a film having a thickness of about 10 μm to 13 mm.

[Lactic acid resin]
In the present invention, the lactic acid-based resin (A) means a polymer containing L-lactic acid and / or D-lactic acid as a main constituent and a polymer composition containing it as a main component. Is a polymer composition containing as a main component a polymer containing at least 50 mol% or more, preferably 75 mol% or more. Synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide, a cyclic dimer of lactic acid, with other monomers copolymerizable with lactic acid within a range that does not significantly impair the properties of the polymer, etc. A composition in which a resin, an additive and the like are mixed may be used. Of the lactic acid resins (A), polylactic acid is preferred. When the component of the L-form or D-form increases as polylactic acid, the heat resistance and the like are improved, so the amount of the L-form is 90 mol% or more, more preferably 95 mol% or more, and most preferably 98 mol% or more. . Alternatively, the amount of Form D is 90 mol% or more, more preferably 95 mol% or more, and most preferably 98 mol% or more.

  Monomers that can be copolymerized with lactic acid include hydroxycarboxylic acids (eg, glycolic acid, caproic acid, etc.), aliphatic polyhydric alcohols (eg, butanediol, ethylene glycol, etc.) and aliphatic polycarboxylic acids (eg, succinic acid). Acid, adipic acid, etc.). When the lactic acid resin (A) is a copolymer, the copolymer may be arranged in any manner such as a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. Furthermore, these are at least partially ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol / propylene glycol copolymer, 1,3-butanediol, 1,4-butanediol. Bifunctional or higher polyhydric alcohols such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, glycerin, trimethylolpropane , Xylene diisocyanate, polyisocyanate such as 2,4-tolylene diisocyanate and the like, and cellulose, polysaccharides such as acetyl cellulose and ethyl cellulose may be copolymerized, at least a part of Linear, cyclic, branched, star-shaped, three-dimensional network structure, any of the structures of may take an equal, there is no limit.

  The lactic acid-based resin (A) is obtained by subjecting the above raw materials to direct dehydration polycondensation or a cyclic dimer of the above lactic acid or hydroxycarboxylic acid, for example, a cyclic ester intermediate such as lactide, glycolide, or ε-caprolactone. Obtained by a method of ring-opening polymerization.

  When producing by direct dehydration polycondensation, the raw materials lactic acid or lactic acids and hydroxycarboxylic acids, aliphatic dicarboxylic acids and aliphatic diols are preferably azeotroped in the presence of an organic solvent, particularly a phenyl ether solvent. Polymerization is carried out by a method of dehydrating and condensing, particularly preferably removing the water from the azeotropic solvent to return the solvent to a substantially anhydrous state. The weight average molecular weight of the lactic acid resin (A) is from 50,000 to 1,000,000, preferably from 80,000 to 500,000, and more preferably from 100,000 to 300,000. Within this molecular weight range, heat resistance, impact strength, strength, moldability, and workability are good.

[Polypropylene resin]
As the polypropylene resin (B) used in the present invention, those produced by a known method can be used. For example, the polypropylene resin (B) is produced by slurry polymerization, gas phase polymerization or liquid phase bulk polymerization using a highly stereoregular catalyst. As the polymerization method, either batch polymerization or continuous polymerization can be employed.

  The polypropylene resin (B) according to the present invention contains at least 1%, preferably 10% or more, more preferably 50% or more, particularly preferably 75% or more as a constituent unit of propylene. As the α-olefin, ethylene or an α-olefin having 4 to 20 carbon atoms, specifically, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene is used. 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4 -Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like. These can also be used individually by 1 type and can also be used in combination of 2 or more type.

  In the present invention, a polypropylene resin (B) having a melt flow rate (MFR: ASTM D1238; measured at 230 ° C. under a load of 2.16 kg) of more than 1 g / 10 minutes and 150 g / 10 minutes or less is used. This MFR is preferably 2 to 100 g / 10 min, more preferably 4 to 80 g / 10 min.

  In the present invention, the polypropylene resin (B) having the above MFR value is preferably a homopolypropylene and / or a propylene block copolymer, containing 0.1 to 40% by weight of an n-decane soluble component, It may be contained in an amount of preferably 0.1 to 35% by weight, particularly preferably 0.1 to 30% by weight.

  The amount of the 23 ° C. decane-soluble component of the polypropylene resin (B) is measured as follows. A 1 liter flask is charged with 3 g of a sample (polypropylene resin), 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500 ml of n-decane and heated at 145 ° C. to dissolve. Cool to 23 ° C over 8 hours after dissolution and maintain at 23 ° C for 8 hours. The precipitated solid and the n-decane solution containing the dissolved polymer are separated by filtration with a glass filter. The liquid phase is dried at 150 ° C. under reduced pressure to a constant weight, and its weight is measured. The obtained polymer dissolution amount is calculated as a percentage with respect to the weight of the sample, and is defined as the 23 ° C. decane soluble amount of the polypropylene resin (B).

The crystallinity of this polypropylene resin (B) is such that the isotactic-pentad fraction [I ₅ ] of its 23 ° C. decane insoluble component is 0.95 to 0.99, preferably 0.96 to 0.99. It is desirable. This pentad isotacticity can be determined by a conventional method from a ¹³ C-NMR spectrum of a 23 ° C. decane insoluble component.
When the polypropylene resin (B) is a propylene block copolymer, the decane soluble component at 23 ° C. is 4 to 40% by weight, preferably 4 to 35% by weight, more preferably 4 to 30% by weight. It is desirable to contain by quantity.

  Further, the polypropylene resin (B) used in the present invention is a branched olefin such as 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1 -Pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl -1-hexene, 3-ethyl-1-hexene, 3,5,5-trimethyl-1-hexene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylnorbornane, allylnorbornane, styrene, dimethylstyrene, allylbenzene, A homopolymer or copolymer such as allyltoluene, allylnaphthalene or vinylnaphthalene is contained as a prepolymer in an amount of 0.1% by weight or less, preferably 0.05% by weight or less. It may be in. Of these, 3-methyl-1-butene is particularly preferable. Prepolymers derived from such branched olefins act as nucleating agents for polypropylene, so that the isotactic pentad fraction (mmmm fraction) can be increased and the moldability can be improved. Can do.

  As the nucleating agent other than the prepolymer, various conventionally known nucleating agents such as phosphate nucleating agents, sorbitol nucleating agents, metal salts of aromatic carboxylic acids, metal salts of aliphatic carboxylic acids, rosin An organic nucleating agent such as an organic compound and / or an inorganic nucleating agent such as an inorganic compound can be used without particular limitation. Specifically, NA-11UY (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), which is a metal salt of organophosphate, and Pine Crystal KM160 (trademark, manufactured by Arakawa Chemical Co., Ltd.), which is a rosin-based nucleating agent. . A nucleating agent can also be used individually by 1 type, and can also be used in combination of 2 or more type. The blending amount of the nucleating agent is usually 0 to 1% by weight, preferably 0.1 to 0.5% by weight, as the blending amount in the polypropylene resin (B) of the present invention.

  The polypropylene resin (B) used in the present invention contains the following antioxidant and / or a non-alkali metal salt component of a fatty acid for suppressing glass fogging, preventing heat deterioration, and improving processing stability and durability. You may make it contain. The containing method is not particularly limited, but it can usually be mixed with polymerized powder and then melt kneaded with an extruder.

  A well-known thing can be used as antioxidant which can be contained in the polypropylene resin (B) used by this invention. Preferably, it is a hindered phenol antioxidant, and more preferably a hindered phenol antioxidant having a melting point of 105 ° C. or higher. Hindered phenol antioxidants having a melting point of 105 ° C. or higher include pentaerythrityl-tetrakis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′— Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, (2,2′-methylenebis [4-methyl-6-tert-butylphenol]), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2 4,8,10- tetra-oxa-spiro [5,5] undecane and the like can be mentioned. It is preferable to use 0.01 to 0.5 parts by weight, particularly 0.03 to 0.2 parts by weight, per 100 parts by weight of the polypropylene resin (B).

  The non-alkali metal salt of a fatty acid that can be contained in the polypropylene resin (B) used in the present invention is preferably a non-alkali metal salt of a fatty acid having a molecular weight of 600 or more and a melting point of 110 ° C. or more. Non-alkali metal salts of fatty acids having a molecular weight of 600 or more and a melting point of 110 ° C. or more include aluminum stearate, calcium stearate, zinc stearate, aluminum oleate, calcium behenate, magnesium behenate, zinc behenate, 1, Examples thereof include calcium 2-hydroxystearate, magnesium 1,2-hydroxystearate, and zinc 1,2-hydroxystearate. It is preferable to use 0.01 to 1 part by weight, particularly 0.04 to 0.5 part by weight, per 100 parts by weight of the polypropylene resin (B).

[Aromatic vinyl / conjugated diene block copolymer modified with polar functional group]
The aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group used in the present invention is a block copolymer (X) derived from an aromatic vinyl and a block copolymer derived from a conjugated diene. An aromatic vinyl / conjugated diene block copolymer comprising a polymer (Y) having a polar reactive group.

  Examples of the aromatic vinyl forming the block copolymer (X) derived from the aromatic vinyl include styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene, 4-propylstyrene, and 4-dodecylstyrene. Examples include 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. Of these, styrene is preferred.

  Examples of the conjugated diene forming the block polymer unit (Y) derived from the conjugated diene include butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. These may be used alone or in combination of two or more. Of these, butadiene or isoprene or a combination of butadiene and isoprene is preferred.

  Further, the conjugated diene block polymer unit (Y) composed of a butadiene / isoprene copolymer unit may be any of a random copolymer unit, a block copolymer unit, or a tapered copolymer unit of butadiene and isoprene.

  The aromatic vinyl / conjugated diene block copolymer comprising the block copolymer (X) derived from aromatic vinyl and the block copolymer (Y) derived from conjugated diene used in the present invention is, for example, aromatic The vinyl block copolymer (X) exists as a crosslinking point of the conjugated diene rubber block copolymer (Y) to form a physical crosslink, and the conjugate existing between the aromatic vinyl block units (X). The diene block unit (Y) is a soft segment and has rubber elasticity. Specifically, polystyrene-polybutadiene, polyisoprene, or polyisoprene-butadiene-polystyrene block copolymer is preferable.

The aromatic vinyl / conjugated diene block copolymer comprising the block copolymer (X) derived from the aromatic vinyl and the block copolymer (Y) derived from the conjugated diene is represented by X (YX) _n or (XY ) _N [n is an integer of 1 or more]. Of these, X (YX) _n, particularly in the form of XYX is preferred.

  The aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group used in the present invention is an aromatic vinyl / conjugated diene block copolymer having a polar functional group, and is obtained by a known utility method. be able to.

  The polar functional group is preferably a base. Further, among basic functional groups, an amino group and an imino group are particularly preferable. You may have 1 type, or 2 or more types of basic functional groups. Specifically, imine-modified SBS (C1) having an imino group as a functional group, imine-modified SBBS (C2), and imine-modified SEBS (C3) are preferable.

  The aromatic vinyl / conjugated diene block copolymer (C) modified with the polar functional group used in the present invention may be used as it is, or hydrogenated by adding hydrogen to the remaining aliphatic double bond. A block copolymer may be used. A known method may be used as the hydrogenation method, and the hydrogenation rate is not particularly limited.

  The aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group used in the present invention has an aromatic vinyl block polymer unit (X) content of 15% by weight or more, preferably 15 to It is contained in an amount of 50% by weight, and MFR (230 ° C., 2.16 kg under load) is 1 to 50 g / 10 min, preferably 2 to 30 g / 10 min.

  As the aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group used in the present invention, those produced by a publicly known method can be used. For example, a method described in JP-A-2003-313255 may be used. Examples of commercially available products generally include N503 and N501 available from Asahi Kasei Corporation.

  The thermoplastic resin composition according to the present invention comprises 10 to 90 parts by weight, preferably 30 to 70 parts by weight of the lactic acid resin (A), and 90 to 10 parts by weight of the polypropylene resin (B), preferably 70 to 30 parts. Parts by weight (however, the sum of (A) and (B) is 100 parts by weight) and aromatic vinyl / conjugated diene block copolymer (C) modified with polar functional groups (A) and (B) 1 to 30 parts by weight, preferably 4 to 20 parts by weight, based on 100 parts by weight.

  When the melt viscosity of the lactic acid resin (A) and the polypropylene resin (B) used in the present invention is combined under the range of the formula (1), the average dispersed particle diameter of the island phase of the thermoplastic resin composition according to the present invention Becomes 1 μm.

Here, Z (A) is the melt viscosity of the lactic acid resin (A) at 200 ° C. and a shear rate of 1216 sec ⁻¹ , and Z (B) is 200 ° C. of the polypropylene resin (B) and a shear rate of 1216 sec ^{−. 1} is the melt viscosity under ¹ . When the value of the formula (1) is 3 or more and 6 or less, the thermoplastic resin composition according to the present invention has a small dispersed particle diameter of the island phase, a good appearance, and a molded product excellent in peeling resistance. It is done.

The measurement of the melt viscosity was carried out under the following conditions according to a conventional method using a Capillograph: Model 1C manufactured by Toyo Seiki Co., Ltd. When the resin was melted in a cylinder at 200 ° C. for 6 minutes and extruded using a capillary with a length of 30 mm and a diameter of 1 mm at a rate of 100 mm / min, the shear rate was 1216 sec ⁻¹ , The melt viscosity was measured at

  The thermoplastic resin composition according to the present invention may be added with publicly known inorganic fillers, rubbers, and compatibilizers as long as the desired physical properties are not lowered depending on the application.

[Inorganic filler]
As the inorganic filler (D), publicly known and generally used ones can be added. Specific examples include talc, silica, mica, calcium carbonate, glass fiber, glass beads, barium sulfate, magnesium hydroxide, wollastonite, calcium silicate fiber, carbon fiber, magnesium oxysulfate fiber, and potassium titanate fiber. , Titanium oxide, calcium sulfite, white carbon, clay, montmorillonite, calcium sulfate and the like. An inorganic filler (D) can also be added 1 type or in combination of 2 or more types. Among the inorganic fillers (D), glass fiber, carbon fiber, mica, talc, calcium carbonate, and titanium oxide are preferable, but talc and titanium oxide are particularly preferable. When talc is used, the heat resistance and impact strength of the obtained molded product are increased, and therefore talc is preferably used. Moreover, since the external appearance like paper is shown in the sheet | seat obtained when a titanium oxide is used, it is used preferably. In particular, when talc and titanium oxide having an average particle diameter of 0.1 to 5 μm, preferably 0.5 to 4 μm are used, it is desirable because a molded product having an excellent appearance can be obtained. 10 to 90 parts by weight of the lactic acid resin (A) of the thermoplastic resin composition according to the present invention, 10 to 90 parts by weight of the polypropylene resin (B) (however, the total of (A) and (B) is 100 parts by weight) The amount of the inorganic filler (D) added is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

[rubber]
In order to improve the impact strength, a publicly known rubber can be added to the thermoplastic resin composition according to the present invention. Specifically, rubber components such as ethylene / α-olefin copolymer rubber, conjugated diene rubber, styrene rubber or biodegradable ester rubber can be blended in an appropriate amount. Specific examples of such rubber (E) include non-diene-containing amorphous materials such as ethylene / 1-butene copolymer rubber, ethylene / 1-octene copolymer rubber, and propylene / ethylene copolymer rubber. Or low crystalline α-olefin copolymer; ethylene / propylene / dicyclopentadiene copolymer rubber, ethylene / propylene / 1,4-hexadiene copolymer rubber, ethylene / propylene / cyclooctadiene copolymer rubber, ethylene / propylene Specific examples of ethylene / propylene / non-conjugated diene copolymer rubbers such as propylene / methylene norbornene copolymer rubber and ethylene / propylene / ethylidene norbornene copolymer rubbers;・ Butadiene-styrene SBS rubber, styrene-butadiene Butylene / styrene-based SBBS rubber, styrene / ethylene / butylene / styrene-based SEBS rubber, modified with acid, etc., maleated modified SBS, maleated modified SBBS, maleated modified SEBS, biodegradable ester system Specific examples of the rubber include polybutylene succinate, polybutylene terephthalate adipate, and their isocyanate cross-linked products. A rubber | gum can also be used 1 type or in combination of 2 or more types. Styrene / ethylene / butylene / styrene-based SEBS and styrene / butadiene / butylene / styrene-based SBBS are desirable as the thermoplastic resin composition having an excellent balance of heat resistance and impact strength. 10 to 90 parts by weight of the lactic acid resin (A) of the thermoplastic resin composition according to the present invention, 10 to 90 parts by weight of the polypropylene resin (B) (however, the total of (A) and (B) is 100 parts by weight) The amount of rubber added is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

[Compatibilizer]
The compatibilizing agent shown in the present invention improves the compatibility of the lactic acid resin (A) and the polypropylene resin (B) used in the present invention, and the island phase dispersion diameter of the thermoplastic resin composition according to the present invention. Is to make it smaller. In addition to the aromatic vinyl / conjugated diene block copolymer (C) modified with the polar functional group used in the present invention, known and publicly used ones can be used. For example, as a block copolymer having a group compatible with both the lactic acid resin (A) and the polypropylene resin (B) used in the present invention, and generally commercially available, Sumitomo Chemical having an epoxy group ( Bond First E commercially available from Co., Ltd., Modiper A4200 commercially available from Nippon Oil and Fats Co., Ltd. having a glycidyl group, and Tuffmer MH7010 commercially available from Mitsui Chemicals Co., Ltd. having a carboxyl group. Furthermore, the compatibilizers (F1) to (F3) shown below can also be used.

  The compatibilizer (F1) shown in the present invention is a product obtained by reacting a polypropylene resin (b1) into which a carbodiimide group-reactive group is introduced into the polypropylene resin (B) and a carbodiimide group-containing compound. It can be obtained by a publicly known method.

  Examples of the compound having a group that reacts with a carbodiimide group include a compound having a group having an active hydrogen having reactivity with a carbodiimide group. Specifically, a group derived from a carboxylic acid, an amine, an alcohol, a thiol, or the like is used. It is a compound possessed. Among these, compounds having groups derived from carboxylic acids are preferably used, and among them, unsaturated carboxylic acids and / or derivatives thereof are particularly preferable. In addition to a compound having a group having an active hydrogen, a compound having a group that can be easily converted into a group having an active hydrogen by water or the like can be preferably used. Specifically, it has an epoxy group or a glycidyl group. Compounds. In the present invention, one or more compounds having a group that reacts with a carbodiimide group may be used.

  In the present invention, when an unsaturated carboxylic acid and / or a derivative thereof is used as a compound having a group that reacts with a carbodiimide group, an unsaturated compound having one or more carboxylic acid groups, an unsaturated compound having one or more carboxylic anhydride groups, and Derivatives thereof can be mentioned, and examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Specific compounds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2 Examples thereof include unsaturated carboxylic acids such as -ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (for example, acid halides, amides, imides, and esters). Specific examples of the compound include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -Dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like.

  Among the carboxylic acid derivatives, maleic anhydride, (meth) acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Products, hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate. Furthermore, it is a dicarboxylic anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride. It is particularly preferred. These may be used alone or in combination of two or more.

As a method for introducing a compound having a group that reacts with a carbodiimide group into the polypropylene resin (B), a publicly known one can be used, for example, a compound having a group that reacts with a carbodiimide group in the polypropylene resin (B). A method of graft copolymerization, a method of radical copolymerization of a compound having a group that reacts with an olefin and a carbodiimide group, and the like can be used.
The content of the compound having a group that reacts with the carbodiimide group in the polypropylene resin (b1) introduced with a group that reacts with the carbodiimide group used in the present invention is 0.1 to 10% by weight, preferably 0.1%. It is -3.0 weight%, More preferably, it is 0.1-1.0 weight%.

  The carbodiimide group-containing compound used in the present invention includes a polycarbodiimide having a repeating unit represented by the following general formula (2).

〔式中、Ｒ１は２価の有機基を示す〕

[Wherein R1 represents a divalent organic group]

  The carbodiimide group-containing compound used in the present invention may contain monocarbodiimide in polycarbodiimide, or a single compound or a mixture of plural compounds may be used. Polycarbodiimide can be synthesized by a publicly known method. For example, a polycarbodiimide can be synthesized by reacting an organic polyisocyanate in the presence of a catalyst that promotes a carbodiimidization reaction of an isocyanate group.

  The number average molecular weight (Mn) in terms of polystyrene determined by gel permeation chromatography (GPC) of the carbodiimide group-containing compound used in the present invention is usually 400 to 500,000, preferably 1,000 to 10,000, more preferably. Is 2,000 to 4,000.

  A commercially available carbodiimide group-containing compound can be used as it is. As a commercially available carbodiimide group containing compound (b), Nisshinbo Co., Ltd. carbodilite HMV-8CA, LA1, etc. are mentioned, for example.

  The compatibilizer (F1) of the present invention can be obtained by reacting a propylene resin (b1) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound. Specifically, it can be obtained by melt-kneading such as melt modification, but is not limited to this method.

  The progress of the reaction between the group that reacts with the carbodiimide group in the compatibilizer (F1) used in the present invention and the carbodiimide group can be investigated by the following method.

After preparing a hot press sheet of a propylene resin (b1) having a group that reacts with a carbodiimide group and a compatibilizer (F1) used in the present invention, an infrared absorption chart is measured using an infrared absorption analyzer. From the obtained chart, absorption due to the peak intensity of the propylene resin (b1) having a group that reacts with a carbodiimide group and the compound having a group that reacts with a carbodiimide group in the compatibilizer (F1) used in the present invention. The absorbance of the band (1790 cm ^-1 when maleic anhydride is used) is measured, the absorbance before and after the reaction with the carbodiimide group-containing compound is compared, and the reaction rate can be calculated using the following formula.

  The reaction rate calculated | required by the said method about the compatibilizer (F1) of this invention is 40 to 100%, Preferably it is 50 to 100%, More preferably, it is 90 to 100%.

  In producing the compatibilizing agent (F1) of the present invention, the compounding amount of the carbodiimide group-containing compound was such that the propylene-based resin (b1) having a group that reacts with the carbodiimide group and the carbodiimide group-containing compound (b) were reacted. The carbodiimide group content is usually 1 to 200 mmol, preferably 10 to 150 mmol, and more preferably 30 to 100 mmol with respect to 100 grams of the resin composition.

  The compatibilizer (F2) according to the present invention is a copolymer having a structure in which the lactic acid resin (A) and the propylene resin (B) are bonded in a block form and / or a graft form via a covalent bond. is there.

  The molecular weight of the compatibilizer (F2) according to the present invention can be measured by a known method. For example, it can be measured by gel permeation chromatography (GPC) using 1,2-dichlorobenzene as a solvent. The copolymer composition ratio between the lactic acid resin (A) and the propylene resin (B) in the compatibilizer (F2) can be known by a known method. For example, it can be known by dissolving the copolymer in deuterated 1,2-dichlorobenzene and measuring the proton NMR spectrum at 120 ° C. From the molecular weight of the compatibilizer (F2) and the composition ratio of each segment, the molecular weight of each segment can be known. For example, when the number average molecular weight of the copolymer is 40,000 and the composition ratio of the lactic acid resin (A) to the propylene resin (B) is 1: 1, the molecular weight of the lactic acid resin (A) is The molecular weight of 20,000 propylene-based resin (B) is 20,000.

  In the production method of the compatibilizer (F2) shown in the present invention, a publicly known method can be used. For example, a monomer containing lactide or lactic acid as a main component is polymerized in the presence of a propylene-based resin (b2) containing a hydroxyl group.

  The propylene-based resin (b2) containing a hydroxyl group used in the present invention is a graft-modified polyolefin resin obtained by graft-polymerizing a vinyl monomer having a hydroxyl group to the propylene-based resin (B). The graft amount of the vinyl monomer having a hydroxyl group is 0.1 to 10% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 10% by weight, based on the total of the propylene resin and the vinyl monomer.

  Examples of the vinyl monomer having a hydroxyl group to be grafted to the propylene resin (B) include 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxypropyl acrylate. Can do. Of these, 2-hydroxyethyl methacrylate (HEMA) is most preferred. The vinyl monomer which has a hydroxyl group can also be used 1 type or in combination of 2 or more types.

  A known method can be used to produce the hydroxyl group-containing polypropylene resin (b2) used in the present invention, but after mixing the propylene resin (B), the hydroxyl group-containing vinyl monomer and the radical polymerization initiator. For example, it can be melt-kneaded with an extruder.

  Specific examples of the radical polymerization initiator used for graft polymerization of a vinyl monomer having a hydroxyl group on the propylene resin (B) include 3,5,5-trimethylhexanoyl peroxide (1) and octanoyl peroxide. (2), decanoyl peroxide (3), lauroyl peroxide (4), succinic acid peroxide (5), acetyl peroxide (6), t-butylperoxy (2-ethylhexanoate) (7), m-toluoyl Peroxide (8), benzoyl peroxide (9), t-butylperoxyisobutyrate (10), 1,1-bis (t-butylperoxy) 3,5,5-trimethylcyclohexane (11), 1,1-bis (T-butylperoxy) cyclohexane (12), t-butylperoxymaleic acid (13) t-butylperoxylaurate (14), t-butylperoxy-3,5,5-trimethylcyclohexanoate (15), cyclohexanone peroxide (16), t-butylperoxyisopropyl carbonate (17), 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane (18), t-butylperoxyacetate (19), 2,2-bis (t-butylperoxy) butane (20), t-butylperoxybenzoate (21), n-butyl-4,4-bis (t-butylperoxy) valerate (22), di-t-butylperoxyisophthalate (23), methyl ethyl ketone peroxide (24), α, α'-bis (t-butylperoxyisopropyl) ) Benzene (25), dicumyl peroxide (26), 2,5-dimethyl-2,5-di (t- Tylperoxy) hexane (27), t-butylcumyl peroxide (28), diisopropylbenzene hydroperoxide (29), di-t-butyl peroxide (30), p-menthane hydroperoxide (31), 2,5-dimethyl -2,5-di (t-butylperoxy) hexyne-3 (32), 1,1,3,3-tetramethylbutyl hydroperoxide (33), 2,5-dimethylhexane-2,5-dihydroperoxide ( 34), cumene hydroperoxide (35), t-butyl hydroperoxide (36) and the like. Among these, the compounds (12) to (36) are particularly preferable.

  The amount of the radical polymerization initiator (g) is 0.01 to 10 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the vinyl monomer (f) having a hydroxyl group. The amount is preferably 5 parts by weight.

  As other monomers other than the lactide and lactic acid, cyclic esters (lactones) such as caprolactone, propiolactone and butyrolactone, and hydroxyalkanoic acids such as hydroxybutanoic acid and hydroxypropanoic acid can be used.

  In the production method of the compatibilizer (F2) shown in the present invention, when the lactide or lactic acid is polymerized in the presence of the polypropylene resin (b2) containing the hydroxyl group, known catalysts and production methods are used. Can be used. The catalyst is preferably a tin catalyst or an aluminum catalyst. More preferably, tin octoate is used, the amount being 0.01 to 5% by weight with respect to lactide.

  The polymerization temperature is appropriately selected from the range of 60 ° C to 230 ° C. Preferably, it is 100 degreeC-200 degreeC. For example, when xylene is used as a solvent and lactide is reacted with a modified polyolefin resin using tin octoate as a catalyst, the reaction temperature is preferably about 110 to 150 ° C.

In the present invention, the compatibilizing agent (F3) is a structure in which a resin containing an acrylic unit as a constituent component and a propylene-based resin (B) are bonded in a block shape and / or a graft shape and / or a random shape via a covalent bond. It is a copolymer having.
In a resin containing an acrylic unit as a constituent component, it is necessary to contain at least 50 mol% or more of acrylic units, and it is preferable to contain 75 mol% or more. As the acrylic unit, an acrylic acid unit is preferable, and preferred examples include a methyl methacrylate unit, a methyl acrylate unit, an ethyl acrylate unit, and a butyl acrylate unit. A plurality of these constituent components may be contained.

  The copolymer composition ratio of the resin containing the acrylic unit in the compatibilizer (F3) as a constituent component and the propylene-based resin (B) can be known by a known method. For example, it can be known by dissolving the compatibilizer (F3) in deuterated 1,2-dichlorobenzene and measuring the proton NMR spectrum at 120 ° C. The composition of the compatibilizer (F3) can be appropriately changed depending on the purpose. In the composition, the weight ratio of the segment (e) containing an acrylic unit as a constituent component to the propylene-based polyolefin segment (a) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20.

  The molecular weight of the compatibilizer (F3) can be measured by a known method. For example, it can be measured by gel permeation chromatography (GPC) using 1,2-dichlorobenzene as a solvent.

  From the molecular weight of the compatibilizer (F3) and the composition ratio of each segment, the molecular weight of each segment can be known. For example, when the weight average molecular weight of the compatibilizer (F3) is 40,000, and the composition ratio of the propylene-based resin (B) to the resin containing the acrylic unit as a constituent component is 1: 1 by weight, The weight average molecular weight of the resin containing an acrylic unit as a constituent component is 20,000, and the weight average molecular weight of the propylene-based resin (B) is 20,000. Although there is no restriction | limiting in particular in the weight average molecular weight of a compatibilizing agent (F3), Preferably it is 2000 or more and 200,000 or less, More preferably, it is 10,000 or more and 100,000 or less.

(Production of polypropylene having a hydroxyl group at the terminal position)
Polypropylene ([η] = 7.6) manufactured by Mitsui Chemicals Co., Ltd. was pyrolyzed at 360 ° C. in a nitrogen atmosphere using a plastmill. The number average molecular weight (Mn) of the polymer obtained by the treatment was 26500 g / mol based on the molecular weight measurement by gel permeation chromatography (GPC). As a result of IR analysis, 0.74 vinylidene groups were present per polymer chain.

  25.0 g of this terminal vinylidene group-containing polypropylene was placed in a 1000 ml glass reactor sufficiently purged with nitrogen, 800 ml of decane and 6 mmol of diisobutylaluminum hydride were added, and the mixture was heated and stirred at 140 ° C. for 6 hours. While keeping the decane solution at 140 ° C. and continuously supplying dry air at a flow rate of 200 liters / h for 6 hours, 10 ml of isobutyl alcohol was added at a solution temperature of 100 ° C. The reaction solution was added to a methanol (1.5 L) / acetone (1.5 L) mixed solution containing 50 ml of 1N hydrochloric acid to precipitate a polymer, and the polymer recovered by filtration was dried at 80 ° C. under reduced pressure for 10 hours. As a result, 24.8 g of a polymer was obtained. As a result of NMR analysis, a hydroxyl group was present at the polymer end, and 40% of the polymer one end was a hydroxyl group.

(Production of terminal-esterified polypropylene having radical polymerization initiation terminal)
57.4 g of the terminal hydroxyl group-containing polypolypropylene obtained above was put into a 1 L 2-neck eggplant flask purged with degassed nitrogen, and 500 ml of dry toluene, 4.1 ml of triethylamine, and 3.1 ml of 2-bromoisobutyryl bromide were added. The mixture was heated to 80 ° C. and stirred for 3 hours.

  After adding 20 ml of methanol to the slurry reaction mixture and cooling to room temperature, the polymer was filtered through a glass filter. At this time, the polymer on the glass filter was sequentially washed twice with 100 ml of methanol, twice with 100 ml of 1N hydrochloric acid, twice with 100 ml of pure water, and twice with 100 ml of methanol. The polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours. As a result of 1H-NMR, a polymer in which the terminal hydroxyl group was esterified was obtained.

  As a method for producing the compatibilizing agent (F3), a 500 mL glass reactor equipped with a Dimroth and a stirring rod was sufficiently substituted with nitrogen gas, and 28.8 g of the above-mentioned esterified polypropylene, methyl methacrylate (MMA) 30. 3 ml and 98.2 ml of o-xylene were added and the temperature was raised to 120 ° C. with slow stirring. In another nitrogen-substituted Schlenk bottle, 100 mg of copper (I) bromide, 0.63 ml of 2M o-xylene solution of N, N, N ′, N ″, N ″ -pentamethyldiethyltriamine, 5.0 ml of o-xylene The homogeneous solution in which MMA was mixed was introduced into an evaporator, the temperature was raised to 120 ° C., and polymerization of MMA was started while stirring at 350 rpm.

After 7.0 hours, 150 ml of toluene was added for dilution, 20 ml of isobutyl alcohol was added, and the mixture was cooled to room temperature. The polymerization mixture was poured into 1.5 L of methanol to precipitate a polymer. The precipitated polymer was filtered off with a glass filter, washed twice with 20 ml of methanol, and dried under reduced pressure conditions of 80 ° C. and 15 Torr for 10 hours.
From the result of nuclear magnetic resonance (NMR) analysis, a polypropylene-polymethyl methacrylate block copolymer (F3) having 36.3 wt% methyl methacrylate segments and containing about 33 wt% unreacted homopolypropylene was obtained. It was.

  The thermoplastic resin composition of the present invention can be added with other additives depending on the use within a range not impairing the object of the present invention. For example, stabilizers (antioxidants, ultraviolet absorbers, Light stabilizers, etc.), flame retardants (bromine flame retardants, phosphorus flame retardants, melamine compounds, etc.), lubricants, mold release agents, antistatic agents, surface wetting improvers, colorants including dyes and pigments, crystal nucleating agents (Organic crystal nucleating agents / organic carboxylic acid metal salts, etc.) Crystallization accelerators, plasticizers, antiblocking agents, antistatic agents, antifogging agents, endblockers (epoxy compounds, oxazoline compounds, carbodiimide compounds), other resins Etc. can be added. These additives can be used alone or in combination of two or more.

  As the crystal nucleating agent used in the present invention, those having known utility can be used. Organic crystal nucleating agents and organic carboxylic acid metal salts are preferred. The organic crystal nucleating agent is preferably an organic compound containing an aliphatic carboxylic acid amide having an amide bond. Specifically, C8-30 aliphatic carboxylic acid monoamides such as capric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, behemic acid amide, methylene bis stearic acid amide, ethylene bis lauric acid Amides, ethylene biscapric amide, ethylene bisoleic amide, ethylene bis erucic amide, ethylene bis bemic acid amide, ethylene bisisostearic amide, ethylene bishydroxystearic amide, butylene bis stearic amide, hexamethylene bis Oleic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis oleic acid amido, hexamethylene bis stearic acid amide, hexamethylene bisbemic acid amido, hexamethylene bishydroxy And aliphatic Amito Bu compound having an amide bond in the molecule such as aliphatic carboxylic acids bisamides such as stearic acid Amito Bu.

  In particular, ethylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis oleic acid amide, hexamethylene bisbemic acid amide and the like can be preferably used. The total addition amount of the organic crystal nucleating agent in the present invention is 0.1 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the thermoplastic resin according to the present invention. Preferably, it is 0.2-1.0 weight part.

  In the present invention, among the above organic crystallization nucleating agents, at least one selected from ethylene bis stearamide, ethylene bis laurate, ethylene bis oleate, hexamethylene bis bemic acid amide, Two or more kinds may be combined.

  When the crystallization accelerator in the present invention is added to crystallize the thermoplastic resin containing the organic crystallization nucleating agent according to the present invention by any method, for example, a method of crystallizing by heat treatment, the crystallization rate is increased. It has the effect | action which accelerates | stimulates.

Diphthalic acid derivatives such as di-N-octyl terephthalate, di-2-ethylhexyl terephthalate, dibenzyl terephthalate, diisodecyl terephthalate, ditridecyl terephthalate, diundecyl terephthalate, isophthalate acid derivatives such as dioctyl isophthalate, di-n-butyl Adipic acid derivatives such as adipate and dioctyl idipate, maleic acid derivatives such as di-n-butyl maleate, citric acid derivatives such as tri-N-butyl citrate, itaconic acid derivatives such as monobutyl itaconate, butyl oleate, etc. Low molecular weight compounds such as oleic acid derivatives, ricinol derivatives such as glycerin monocinolate, phosphate esters such as tricresyl phosphate and trixylenyl phosphate, polyethylene adipate, polyester Hydroxy polycarboxylic acid esters such as acrylate array chill tributyl citrate, polyhydric alcohol esters such as gray serine triacetate or grade serine tripropionate, polybutyl glycol,
Examples include polyalkylene glycol derivatives such as polypropylene glycol, benzyl-2- (2-methoxyethoxy) ethyl adipate, and the like.

In particular, citric acid derivatives, polyalkylene glycol derivatives, hydroxy polyvalent carboxylic acid esters, polyhydric alcohol esters, etc., which exhibit the effect of accelerating the crystallization rate in a small amount and are easily available at low cost, are preferably used.

  Polyethylene glycol, ATBC (trade name; manufactured by Jay Plus Co., Ltd.), Daifati 101 (trade name; manufactured by Daihachi Chemical Co., Ltd.), Riquemar PL-710 (trade name; manufactured by Riken Vitamin Co., Ltd.), lact Sizer GP4001 (trade name; manufactured by Arakawa Chemical Co., Ltd.) and the like are relatively inexpensive and easily available and can be preferably used because of their high crystallization promoting effect.

  The addition amount of the crystallization accelerator is 0.5 to 7 parts by weight, more preferably 1 to 5 parts by weight, and further preferably 1 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic resin according to the present invention. .

  As the lubricant used in the present invention, known and publicly used ones can be used. For example, aliphatic hydrocarbon lubricants such as liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyethylene, stearic acid, lauric acid, hydroxy stearic acid, aliphatic lubricants such as hardened castor oil, stearamide, oleic acid Aliphatic amide, oleic amide, oleic amide, erucic amide, lauric acid amide, palmitic acid amide, methylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bisbehemic acid amide, ethylene bis lauric acid amide, etc. Amide lubricants, metal soap lubricants that are aliphatic metal salts having 12 to 30 carbon atoms such as lead stearate, calcium stearate, calcium stearate, long chain ester waxes such as montan sun wax, or the like Include the composite lubricant that combines.

  The amount of the lubricant used is 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, more preferably 0.3 to 1 part by weight based on 100 parts by weight of the thermoplastic resin product according to the present invention. It is.

  A generally known method can be used for the method for producing the thermoplastic resin composition of the present invention. For example, a lactic acid resin (A), a polypropylene resin (B), an aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group and, if necessary, an inorganic filler (D), rubber (E) , A method in which a compatibilizer (F), an additive, and the like are blended in advance and then uniformly melt-kneaded using a single-screw or multi-screw extruder having sufficient kneading ability above the melting point of the resin. . In order to improve dispersion, it is preferable to use a twin screw extruder. Furthermore, a method of mixing and kneading at the time of melting, a method of removing the solvent after mixing in a solution, or the like can also be employed.

  The molded article of the thermoplastic resin composition according to the present invention can be produced by a molding technique such as publicly known extrusion molding, injection molding, calendar molding, blow molding and the like. Furthermore, the heat resistance of the molded product can be further improved by heat-treating the obtained molded product.

  A stretched sheet can also be produced by stretching a sheet obtained by extrusion.

  Further, if necessary, a layer having functions such as antistatic property, antifogging property, tackiness, gas barrier property, adhesion, adhesion and easy adhesion can be formed on the sheet surface by coating. For example, the antistatic layer can be formed by applying and drying an aqueous coating solution containing an antistatic agent on one or both sides of the sheet. In addition, by laminating other resins and other sheets as necessary, functions such as antistatic properties, antifogging properties, tackiness, gas barrier properties, adhesion, adhesiveness, and easy adhesion properties can be formed. . At that time, a known method such as extrusion lamination or dry lamination can be used.

  In addition, the molded product made of the thermoplastic resin composition of the present invention includes automobile parts (interior / exterior parts, etc.), resin parts for electrical appliances such as various cases, building materials, civil engineering materials, furniture members, agricultural materials, and gaming machines. It can be used for various purposes such as materials, tableware, sports materials, musical instruments and daily necessities. For example, various levers as automobile parts, various handles, wheel caps, copy machines, personal computers, printers, electronic musical instruments, home game machines, portable game machines, housing and internal parts, curtain parts, blind parts, roof panels, Dish, cup, spoon, food container, container, cultivation container, golf tee, golf club, shampoo bottle, candy packaging, shrink label, lid material, packaging film, shopping bag, garbage bag, musical instrument, carrier tape, printing sheet , Release sheet, porous sheet, container bag, credit card, cash card, ID card, IC card, draining net, drainage filter, bag, toothbrush, stationery, cooler box, hose nozzle, pen cap, etc. .

  The heat-resistant deformation temperature of the thermoplastic resin composition of the present invention is 60 ° C. or higher, more preferably 70 ° C. or higher and 140 ° C. or lower. This heat-resistant deformation temperature refers to a value measured under a load of 0.45 MPa using a 3.2 mm-thick test piece according to ASTM D648. Further, the high-speed surface impact test value is 1.0 J or more, more preferably 1.0 to 10 J in the case of a square plate having a thickness of 120 mm × 130 mm × 2 mm. This high-speed surface impact test value is a value measured under conditions of a temperature of 23 ° C. and a speed of 3 m / sec using a striker having a tip diameter of 1/2 inch and a 3.0 inch receptacle in accordance with ISO 6603-2. Further, the high-speed surface impact test value when the test piece is a sheet of 120 mm × 130 mm × 200 μm thickness is 480 mJ or more, more preferably 500 mJ or more and 1000 mJ or less. The high-speed surface impact test value is a value measured under conditions of a temperature of 23 ° C. and a speed of 0.06 m / sec using a striker with a tip diameter of 1/2 inch and a 1.0 inch receptacle. The Izod impact strength is 38 j / m or more, more preferably 40 or more and 120 or less. The Izod impact strength is a value measured at a temperature of 23 ° C. using a test piece having a thickness of 3.2 mm and a cutting notch according to ASTM D256. The flexural modulus is 1000 MPa or more, and more preferably 1000 MPa or more and 3000 MPa or less. The flexural modulus here is a value measured under the conditions of a 3.2 mm thick test piece, a span of 50 mm, a bending speed of 1.5 mm / min, and a measurement temperature of 23 ° C. according to ASTM D790.

  The average dispersed particle size of the island phase of the thermoplastic resin composition of the present invention is 1 μm or less, more preferably 0.8 μm or less. The average dispersed particle size was measured by observing the cross section of the molded product with an electron microscope, digitizing the photograph, and performing image processing according to a conventional method.

  The peel resistance test value (cross-cut peel) is 6 or more, preferably 8 or more. This peel resistance test value is based on the adherence of JIS K5400 (cross-cut method), and in the atmosphere of 23 ° C., the surface of the obtained molded product is cut with a cutter at 2 mm intervals in the range of 10 × 10 mm square. Adhesive tape made sufficiently was applied and peeled off at an angle of 90 °. It measured according to the evaluation score of the cross cut test of JIS K5400. Moreover, the storage elastic modulus at 100 ° C. of the sheet made of the thermoplastic resin of the present invention is 20 MPa or more and 3000 MPa or less, and more preferably 50 MPa or more and 2000 MPa or less. This storage elastic modulus refers to a value obtained by measuring a 200 μm sheet test piece under the conditions of a frequency of 1 Hz and a measurement temperature of 0 to 200 ° C. according to A of JIS-K-7198.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In the present invention, various physical properties were measured and evaluated by the following methods.

(1) Appearance Injection molding was performed using the obtained thermoplastic resin composition, and the appearance of the obtained injection molded product was visually observed.

(2) Melt viscosity Capillograph manufactured by Toyo Seiki Co., Ltd .: Model 1C was used, the resin was melted in a cylinder at 200 ° C. for 6 minutes, and a capillary having a length of 30 mm and a diameter of 1 mm was used. The melt viscosity was measured when the shear rate at the time of extrusion was 1216 sec ⁻¹ .

(2) Peel resistance test For the obtained molded product, in accordance with JIS K5400 adhesion (cross-cut method), in a 23 ° C atmosphere, the surface is cut in a 10 x 10 mm square range at intervals of 2 mm with a cutter. Then, a Nichiban adhesive tape was sufficiently applied and peeled off at an angle of 90 °. In accordance with the evaluation score of the cross-cut test of JIS K5400, a score of 10 or more was rated as 8 or more.

  (3) Average dispersed particle size of island phase of thermoplastic resin composition The cross section of the molded product was observed with an electron microscope, the photograph was digitized, and measured by image processing according to a conventional method.

(4) Tensile strength and tensile elongation In the case of an ASTM test piece having a thickness of 3.2 mm according to ASTM D638, the tensile strength and tensile elongation were measured under conditions of a temperature of 23 ° C. and a tensile speed of 10 mm / min. In the case of a sheet, a strip-shaped sheet test piece having a width of 10 mm was used, and measurement was performed under the conditions of a temperature of 23 ° C., a distance between chucks of 50 mm, and a tensile speed of 20 mm / min.

(5) Flexural modulus Using an ASTM test piece having a thickness of 3.2 mm according to ASTM D790, measurement was performed under conditions of a temperature of 23 ° C., a span of 50 mm, and a bending speed of 1.5 mm / min.

(6) Izod impact strength Measured at a temperature of 23 ° C. using an ASTM test piece (cutting notch) having a thickness of 3.2 mm according to ASTM D256.

(7) Heat-resistant deformation temperature Using an ASTM test piece having a thickness of 3.2 mm according to ASTM D648, measurement was performed under conditions of a temperature of 23 ° C. and a load of 0.45 MPa.

(8) High-speed surface impact test Using a 120 mm × 130 mm × 2 mm square plate according to ISO 6603-2, measurement temperature of 23 ° C., tip diameter of 1/2 inch, receptacle of 3.0 inch, speed of 3 m / sec. Measured with
In addition, measurement was performed using a 120 mm × 130 mm × 0.25 mm sheet under the conditions of a measurement temperature of 23 ° C., a tip diameter of 1/2 inch, a receiver of 1 inch, and a speed of 0.06 m / sec.

(9) Storage elastic modulus (E ')
A sheet test piece having a thickness of 200 μm was measured at a frequency of 1 Hz and a temperature of 0 to 200 ° C. based on method A of JIS-K-7198.

[Production Method of Compatibilizer (F1-1)]
As a polypropylene resin (b1-1) having a group that reacts with a carbodiimide group, 100 parts by weight of maleic acid-modified polypropylene (number average molecular weight 30,000, intrinsic viscosity η0.8 g / ml, maleic acid amount 1.1 wt%) A carbodiimide group-containing compound (polycarbodiimide manufactured by Nisshinbo Industries, Inc., trade name: Carbodilite HMV-8CA) is melt-kneaded in a 30 mmφ twin screw extruder set at a cylinder temperature of 250 ° C. (F1-1) was obtained.

  The number average molecular weight (Mn) of the maleic acid-modified polypropylene was measured by gel permeation chromatography (GPC). The intrinsic viscosity η of the maleic acid-modified polypropylene is a value measured in decalin at 135 ° C. The maleic acid amount of the maleic acid-modified polypropylene is purified by dissolving maleic acid-modified polypropylene in hot xylene and then reprecipitating in acetone. The purified product is again dissolved in hot xylene, and then N / 20 concentration After saponifying the grafted monomer by adding an excessive amount of KOH solution (2-propanol), excess KOH is obtained by back titration with an N / 20 concentration HCl solution (2-propanol) using thymol blue as an indicator. Value.

[Example 1]
Polylactic acid (A-1) as a lactic acid-based resin (A) (Mitsui Chemicals, Inc., trade name: H100 weight average molecular weight: 160,000, specific gravity: 1.25, L-form / D-form = 98.7 / 1. 3. Melt viscosity at 200 ° C. · 1216 sec ⁻¹ : 50 parts by weight, polypropylene resin (B-1) as polypropylene resin (B) (measured MFR at 230 ° C .: 60 g / 10 min, specific gravity: 0.1. 91, melt viscosity at 200 ° C. · 1216 sec ⁻¹ : 49 Pa · s), (A-1) / (B-1) melt viscosity ratio = 4.2, imino as basic polar functional group Group-modified aromatic vinyl / conjugated diene block copolymer (C-1) (manufactured by Asahi Kasei: N503, 230 ° C. MFR: 20 g / 10 minutes, specific gravity: 0.91, styrene content: 30 wt%) -1) and (B-1) total 100 weight Talc (D-1) (manufactured by Fuji Talc Kogyo Co., Ltd .; average particle size: 4.2 μm, apparent density: 0.13 g / ml, whiteness: 98.5) %) Is 10 parts by weight with respect to a total of 100 parts by weight of (A-1) and (B-1), and the compatibilizer (F1-1) is 100 in total of (A-1) and (B-1). 5 parts by weight with respect to parts by weight, 0.1 parts by weight of stearic acid (manufactured by Nippon Oil & Fats Co., Ltd .: brand name cherry stearate) with respect to a total of 100 parts by weight of (A-1) and (B-1) The mixture was uniformly blended and melt-kneaded at a cylinder temperature of 180 ° C. using a TEM35BS twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) to obtain a thermoplastic resin composition. Next, with a Ti-80G2 injection molding machine (manufactured by Toyo Machine Metal Co., Ltd.), injection molding is performed under the conditions of a cylinder set temperature of 170 to 200 ° C., a mold temperature of 80 ° C., an injection and pressure holding time of 10 seconds, and a cooling time of 30 seconds An ASTM test piece having a thickness of 3.2 mm was obtained. The island phase at the center of the obtained specimen is polylactic acid, the average dispersed particle system of polylactic acid (A-1) is 0.57 μm, and peeling is seen at 10 points on the surface adhesive tape grid peel test. There wasn't.

[Example 2]
Polylactic acid (A-1) 50 parts by weight, polypropylene resin (B-2) (230 ° C. measurement MFR: 50 g / 10 min, specific gravity: 0.91, amount of components soluble in normal decane: 8%, 200 ° C. Melt viscosity under 1216 sec ⁻¹ : 65 Pa · s) 50 parts by weight, (A-1) / (B-2) melt viscosity ratio = 3.2, aromatic vinyl modified with basic polar functional group The conjugated diene block copolymer (C-1) is 10 parts by weight with respect to a total of 100 parts by weight of (A-1) and (B-2), and talc (D-1) is (A-1) and (B -2) 10 parts by weight relative to a total of 100 parts by weight, compatibilizer (F-1) 5 parts per 100 parts by weight of (A-1) and (B-2), stearic acid 0.1 part was molded by the same method as in [Example 1] with respect to a total of 100 parts by weight of (A-1) and (B-2), and the physical properties were measured. The island phase in the center of the obtained specimen is polylactic acid, the average dispersed particle system of polylactic acid (A-1) is 0.67 μm, and peeling is seen at 10 points in the surface layer adhesive tape cross peel test. There wasn't.

[Comparative Example 1]
Polylactic acid (A-1) 50 parts by weight, polypropylene (B-3) (230 ° C. MFR: 10 g / 10 min, specific gravity: 0.91, melt viscosity under 200 ° C./1216 sec ⁻¹ : 96 Pa · s) 50 parts by weight, (A-1) / (B-3) melt viscosity ratio = 2.2, talc (D-1) 10 for 100 parts by weight of (A-1) and (B-3) in total Styrene / ethylene / butylene / styrene-based SEBS rubber (E-1) (manufactured by Asahi Kasei: H1062, 230 ° C. MFR: 4.5 g / 10 min, specific gravity: 0.89, styrene content : 18 wt%) 10 parts by weight with respect to a total of 100 parts by weight of (A-1) and (B-3), and 0.1 parts with respect to a total of 100 parts by weight of stearic acid (A-1) and (B-3). 1 part was blended in the same way as in [Example 1], then molded and measured for physical properties. . The island phase at the center of the obtained test piece was polylactic acid, the average dispersed particle system of polylactic acid (A-1) was 1.3 μm, and the entire surface was peeled at 0 points on the surface of the adhesive tape.

[Comparative Example 2]
100 parts by weight of polylactic acid (A-1) was molded in the same manner as in Example 1, and the physical properties were measured.

[Example 3]
Polylactic acid (A-2) as lactic acid resin (A) (Mitsui Chemicals, Inc., sales H400 weight average molecular weight: 200,000, specific gravity: 1.25, L isomer / D isomer = 98.7 / 1.3, 200 Melting viscosity under ℃ · 1216 sec ^-1 : 50 parts by weight, polypropylene resin (B-2) as polypropylene resin (B) (230 ° C measured MFR: 50 g / 10 min, specific gravity: 0.91, normal Component amount soluble in decane: 8%, melt viscosity at 200 ° C. · 1216 sec ⁻¹ : 50 parts by weight, melt viscosity ratio of (A-2) / (B-2) = 5.0 , Aromatic vinyl / conjugated diene block copolymer modified with basic polar functional group (C-1) (manufactured by Asahi Kasei: N503, 230 ° C. MFR: 20 g / 10 min, specific gravity: 0.91, styrene content: 30 wt. %) Sum of (A-1) and (B-2) 5 parts by weight are uniformly blended with a mixer with respect to 00 parts by weight. Using a TEM35BS twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), the mixture is melt-kneaded at a cylinder temperature of 180 ° C. and then pelletized to obtain a thermoplastic resin composition. Obtained. Next, the pellets obtained by the above method were supplied to a T-die film forming machine having a cylinder diameter of 220 ° C. and a screw diameter of 50 mm and a die width of 500 mm. The molten resin was extruded onto a cast roll whose temperature was adjusted to 30 ° C. to obtain a sheet having a thickness of 200 μm. By the above methods, tensile strength, tensile elongation, high-speed surface impact test, peel resistance test, average dispersed particle size, storage elastic modulus at 100 ° C., and dispersed particle size of island phase were measured. The island phase in this case was polylactic acid (A-2), and the average dispersed particle size was 0.67 μm.

[Example 4]
50 parts by weight of polylactic acid (A-2) as the lactic acid resin (A), 50 parts by weight of polypropylene (B-2) as the polypropylene resin (B), aromatic vinyl conjugated diene block modified with basic polar functional groups 5 parts by weight with respect to a total of 100 parts by weight of the copolymers (C-1) (A-1) and (B-2), and titanium oxide (D-2) (Ishihara Sangyo Co., Ltd.) as an inorganic filler (D) After the blending of 10 parts by weight with respect to a total of 100 parts by weight of the manufactured product, trade name, Taipei CR-60-2, average particle size 0.21 μm) (A-1) and (B-2), the same as in Example 3 Molded by the method and measured for physical properties. The island phase in this case was polylactic acid (A-2), and the average dispersed particle size was 0.67 μm.

[Example 5]
As an inorganic filler (D), calcium carbonate (D-3) (trade name Softon 1800, average particle diameter 1.25 μm) (A-1) and (B-2) manufactured by Bihoku Powder Chemical Co., Ltd. instead of acid value titanium )) Was used in the same manner as in Example 4 except that 10 parts by weight was used, and the physical properties were measured. The island phase in this case was polylactic acid (A-2), and the average dispersed particle size was 0.67 μm.

[Example 6]
Blended in the same manner as in Example 3 except that 5 parts by weight is changed to 10 parts by weight with respect to 100 parts by weight of the total amount of copolymer (C) (A-1) and (B-2). The physical properties were measured. The island phase in this case was polylactic acid (A-2), and the average dispersed particle size was 0.67 μm.
[Comparative Example 3]
50 parts by weight of polylactic acid (A-2) and 50 parts by weight of a polypropylene resin (B-2) were blended and molded in the same manner as in Example 3, and the physical properties were measured. The island phase became a continuous phase and the dispersed particle size was not measurable.

[Comparative Example 4]
100 parts by weight of polylactic acid (A-2) was molded in the same manner as in Example 3, and the physical properties were measured.

  Obtained from a thermoplastic resin composition comprising a lactic acid resin (A), a polypropylene resin (B) and an aromatic vinyl / conjugated diene block copolymer (C) modified with a polar functional group according to the present invention. Thermoplastic resin moldings have a fine dispersion of PLA of 1 μm or less, a good appearance, excellent peel resistance, and good moldability. Therefore, various types of injection molding, hollow molding, extrusion molding, calendar molding, etc. Can be processed into a molded body. These molded bodies can be used as electrical / electronic parts, automobile interior / exterior products, containers, medical materials, and other various industrial materials.

Claims (7)

    Modified with 10 to 90 parts by weight of a lactic acid resin (A), 90 to 10 parts by weight of a polypropylene resin (B) (however, the sum of (A) and (B) is 100 parts by weight) and a polar functional group A thermoplastic resin composition comprising 1 to 30 parts by weight of the aromatic vinyl / conjugated diene block copolymer (C) based on a total of 100 weights of (A) and (B).     The thermoplastic resin composition according to claim 1, wherein the polar functional group of the aromatic vinyl / conjugated diene block copolymer (C) modified with the polar functional group is a base.     An aromatic vinyl-conjugated diene block copolymer (C) modified with a polar functional group is selected from the group consisting of imine-modified SBS (C1), imine-modified SBBS (C2), and imine-modified SEBS (C3) The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a copolymer of two or more. The melt viscosity of the lactic acid resin (A) and the polypropylene resin (B) at a shear rate of 1216 sec ⁻¹ at 200 ° C. satisfies the range of the following formula (1), and the lactic acid resin (A) 10 to 10 90 parts by weight, 90 to 10 parts by weight of the polypropylene resin (B) (provided that the total of (A) and (B) is 100 parts by weight) and the aromatic vinyl / conjugated diene block modified with a polar functional group A thermoplastic resin composition comprising 1 to 30 parts by weight of the polymer (C) and having an average dispersed particle size of the lactic acid resin (A) of 1 μm or less.

here,
Z (A): Melt viscosity of lactic acid resin (A) at 200 ° C. under a shear rate of 1216 sec ⁻¹ Z (B): Melt viscosity of polypropylene resin (B) at a shear rate of 1216 sec ⁻¹ at 200 ° C.     The molded object which consists of a thermoplastic resin composition of Claims 1-4.     The molded body according to claim 5, wherein the molded body is a sheet.     The test method for temperature dependence of dynamic viscoelasticity (JIS-K-7198, Method A) The storage elastic modulus (E ') at 100 ° C is 20 MPa or more and 3000 MPa or less. Sheet.