JP5315668B2 - Molded product containing biodegradable resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article containing biodegradable resin small in environmental load, maintaining the productivity of an existing polyolefin molded article, and having heat resistance, mechanical characteristics, moisture-proofness, etc. equivalent to or higher in quality than those of an existing article. <P>SOLUTION: The molded article has a layer structure in which a resin layer X formed of a resin composition D, and a resin layer Y formed of a thermoplastic resin composition E are laminated. The resin composition D contains a biodegradable resin composition A, a polyolefinic resin composition B and a dispersant C, and has a sea-island structure in which the biodegradable resin composition A is dispersed as an island component with an average dispersion diameter of 1-1,000 nm in the polyolefinic resin composition B. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a molded article such as a film or fiber containing a biodegradable resin.

  Polyolefin resins typified by polypropylene are inexpensive and excellent in molding processability, and have a good balance of physical properties such as rigidity, and thus are being used in a wide variety of applications. In film applications, it is actively used as a film for wrapping foods such as confectionery, as a film making use of moisture resistance and moisture resistance, and in the form of non-woven fabrics for fibers and sanitary materials such as disposable diapers. However, in recent years, petroleum-derived materials have become a source of biodegradable resins and plant / biological materials due to problems such as depletion of resources, generation of carbon dioxide during production and incineration, and no decomposition after disposal. Attention has been gathered.

  In particular, among the biodegradable resins, polylactic acid-based resins as a group of polyester resin compositions mainly composed of a lactic acid monomer are produced by using a biomass such as corn as a raw material and a lactic acid monomer as a monomer by fermentation using microorganisms. Since it can be manufactured at low cost and can be melt-molded, it is expected to be a biopolymer that can replace resin produced from fossil raw materials such as petroleum. However, further improvement is necessary for practical properties such as heat resistance. is there.

  On the other hand, a technique for blending a plurality of resins is widely known as a polymer alloy technique, and is widely used for the purpose of improving the defects of individual polymers.

  Patent Document 1 discloses a microbial-disintegrating thermoplastic resin composition in which a polyolefin resin is mixed and dispersed in a biodegradable thermoplastic resin, and a part of the polyolefin resin is a modified polyolefin resin. However, Patent Document 1 aims to control microbial disintegration, and does not disclose any properties such as molding processability and heat resistance, and any of the characteristics such as molding processability, heat resistance and mechanical properties. However, there is no suggestion of a solution for obtaining an excellent molded product.

  Patent Document 2 discloses a microbial disintegrating thermoplastic resin film obtained from a composition obtained by blending a compatibilizer with a mixed system of an aliphatic polyester and a polyolefin resin. However, since the sea component is an aliphatic polyester, Patent Document 2 is an invention relating to a film having high microbial disintegration property and heat fusion property, and any of the properties such as molding processability, heat resistance, and mechanical properties. However, there is no suggestion of a solution for obtaining an excellent molded product.

  Patent Document 3 discloses a polyolefin-based resin composition containing a polyolefin-based resin, a polylactic acid-based synthetic resin component, a vinyl acetate / ethylene copolymer, and the like that have improved stable productivity when processed into a sheet-like material. . However, it is an invention aimed at stable productivity when processed into a sheet-like product, and there is no disclosure about heat resistance, and a molded product excellent in all of the properties such as molding processability, heat resistance and mechanical properties. There is no suggestion of a solution to get it.

  Patent Document 4 discloses a biodegradable blend resin obtained by blending a biodegradable resin and a polyolefin resin. However, Patent Document 4 is an invention for the purpose of having high interlayer adhesive strength in a laminated film, and there is no disclosure about characteristics such as heat resistance, and characteristics such as molding processability, heat resistance, and mechanical characteristics. There is no suggestion of a solution for obtaining an excellent molded product.

  Patent Document 5 discloses a biodegradable plastic material obtained by blending a biodegradable polymer, a polymer other than the biodegradable polymer, and a compatibilizer. However, in the invention of Patent Document 5, the effect of improving the heat resistance is insufficient, and there is no suggestion of a solution means for obtaining a molded product having excellent properties such as molding processability, heat resistance and mechanical properties. .

  Patent Document 6 discloses a polylactic acid resin, a crystalline polypropylene resin composition in which the crystalline polypropylene resin contains a modified polypropylene resin, and a polylactic acid resin composition containing an inorganic filler. However, in the invention of Patent Document 6, the effect of improving heat resistance is insufficient, and there is no suggestion of a solution means for obtaining a molded product excellent in all of properties such as molding processability, heat resistance and mechanical properties. .

As described above, no matter which method is used, practical properties such as moldability, heat resistance and mechanical properties cannot be satisfied, and further improvements have been demanded.
JP 05-179110 A Japanese Patent Laid-Open No. 06-263892 Japanese Patent Laid-Open No. 2003-301077 JP 2005-68232 A Japanese Patent Laid-Open No. 2005-248160 JP-A-2005-307128

  The purpose of the present invention is to maintain the productivity of current polyolefin molded products while containing biodegradable resins with low environmental impact, such as polylactic acid, and to have heat resistance, mechanical properties, moisture resistance, etc. equal to or higher than current products. It is to provide a molded product having.

In order to achieve the above object, the present invention has the following configuration. That is, a molded article having a layer structure in which a resin layer (X) made of a resin composition (D) and a resin layer (Y) made of a thermoplastic resin composition (E) are laminated, (D) includes a biodegradable resin composition (A), a polyolefin resin composition (B), and a dispersant (C), and the biodegradable resin composition (A) is a polyolefin resin composition as an island component. (B) the average dispersed diameter is 1nm or more in, have a dispersed island structure below 1,000 nm, the biodegradable resin composition (a), the polyolefin resin composition (B) and dispersing agent (C) When the total weight is 100% by mass,
(1) The content (a) of the biodegradable resin composition (A) is in the range of 4 to 30% by mass,
(2) The content (b) of the polyolefin resin composition (B) is in the range of 56 to 95% by mass,
(3) The content (c) of the dispersant (C) is in the range of 0.1 to 20% by mass,
And,
(4) The mass ratio (a / b) of the content (a) of the biodegradable resin composition (A) and the content (b) of the polyolefin resin composition (B) is 0.05 to 0.42. It is the molded product in the range of.

  According to the present invention, a molded product excellent in heat resistance, mechanical properties, moisture resistance and the like can be obtained, and as a general industrial or packaging material film, a non-woven fabric for food, sanitary material, industrial material, etc. It can be used suitably.

  The resin composition (D) forming the resin layer (X) of the molded product of the present invention is <hereinafter sometimes referred to as (D)>, biodegradable resin composition (A) <hereinafter referred to as (A) In some cases, the polyolefin-based resin composition (B) <hereinafter sometimes referred to as (B)> and a dispersant (C) <hereinafter sometimes referred to as (C)>. Yes.

  In the present invention, it has a sea-island structure in which the biodegradable resin composition (A) is dispersed as an island component (domain) in the polyolefin-based resin composition (B) (matrix). Such a sea-island structure is easily developed when (A) and (B) are incompatible with each other. By taking such a sea-island structure, crystallization of (B) is promoted at the interface between (A) domain and (B) matrix, and this becomes crystal growth nuclei, and (B) the crystallinity of the entire matrix is improved. Conceivable. Furthermore, it is important that the average dispersion diameter of the domain (A) is 1 nm or more and 1,000 nm or less. Preferably, the average dispersion diameter of the domain (A) is 1 nm or more and 800 nm or less, more preferably 1 nm or more and 500 nm or less, and further preferably 1 nm or more and 300 nm or less. When the average dispersion diameter is in such a range, it is considered that (B) the matrix crystallinity improving effect is increased by increasing the area where the (A) domain and the (B) matrix are in contact. (A) When the average dispersion diameter of the domain exceeds 1,000 nm and the average dispersion diameter becomes coarse, not only the above-mentioned crystallinity improvement effect can be obtained, but also the stability in the film forming and spinning process is remarkably lowered. There are concerns.

The phase structure of the resin composition (D) forming the resin layer (X) is confirmed by preparing an ultrathin section of the resin composition (D) using a microtome and using a transmission electron microscope ( A cross-sectional photograph of X) is taken and (A) the short side and long side of the domain observed from the obtained photograph are arithmetically averaged.

  On the other hand, if a molded article using a resin composition comprising only (A) and a molded article comprising a resin composition having a sea-island structure in which (B) domains are dispersed in a matrix (A) are polyolefin films, It is considered difficult to achieve the above water vapor barrier property, and if it is a fiber, it may be inferior in productivity.

  The molded article of the present invention has a composite layer structure in which a resin layer (X) made of a resin composition (D) and a resin layer (Y) made of a thermoplastic resin (E) are laminated. This layer structure may be a two-layer structure of the resin layer (X) and the resin layer (Y), or a three-layer structure or a four-layer structure in which the resin layer (X) or the resin layer (Y) is further laminated. It may have a multilayer structure such as. Particularly preferred is a three-layer structure film having a structure of resin layer (Y) / resin layer (X) / resin layer (Y). Here, for example, in a molded article composed only of the resin layer (X) made of the resin composition (D), the stability such as melt extrusion or stretching may be lowered in a process such as film formation or spinning. In particular, if the shape is a film, the smoothness of the surface is remarkably lowered, so that when used as a deposited film, the water vapor barrier property is greatly deteriorated.

  Examples of the biodegradable resin composition (A) include polylactic acid, polyglycolic acid, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate · 3-hydroxyvalerate), polycaprolactone, or ethylene glycol, Aliphatic polyesters composed of aliphatic diols such as 1,4-butanediol and aliphatic dicarboxylic acids such as succinic acid and adipic acid, and also fats such as poly (butylene succinate terephthalate) and poly (butylene adipate terephthalate) A copolymer of an aromatic polyester and an aromatic polyester, polyvinyl alcohol, and the like.

  Among them, the most preferably used is a polylactic acid resin obtained by polymerizing L-lactic acid and / or D-lactic acid as a main component (monomer component), and a composition containing this polylactic acid resin (polyester resin) is used. It is preferable to use it as the biodegradable resin composition (A). Here, the polylactic acid resin may contain a copolymerization component other than lactic acid, and other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanedio. -Glycol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid , Sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) Tan, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid and other dicarboxylic acids, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycapron Examples thereof include hydroxycarboxylic acids such as acid and hydroxybenzoic acid, and lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  When a polylactic acid resin is used, the molecular weight and molecular weight distribution are not particularly limited as long as they can be substantially extruded, but the mass average molecular weight is usually 10,000 to 500,000, preferably 4 It is 10,000 to 300,000, more preferably 80,000 to 250,000. Here, the mass average molecular weight refers to the molecular weight in terms of polymethyl methacrylate measured by gel permeation chromatography. If the mass average molecular weight is less than 10,000, the molded product may become extremely brittle and may not be suitable for practical use. When the mass average molecular weight exceeds 500,000, the melt viscosity is too high and extrusion is often difficult, and the surface of the molded article may be roughened.

  The melting point of the polylactic acid resin is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, from the viewpoint of heat resistance. The upper limit is not particularly limited, but is usually 190 ° C.

  The polyolefin resin composition (B) used in the present invention includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Unmodified olefin resin obtained by polymerization or copolymerization of olefins such as olefins such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, vinyl alcohol or derivatives thereof And modified polyolefin resins modified with compounds such as unsaturated carboxylic acids or their derivatives and carboxylic acid vinyl esters are not included.

  Specific examples include polyethylene resins, polypropylene resins, poly 1-butene resins, poly 1-pentene resins, poly 4-methyl-1-pentene resins, homopolymers, ethylene / α-olefin copolymers, or these Non-conjugated diene monomers such as 1,4-hexadiene, dicyclopentadiene 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene And a copolymer obtained by copolymerizing one or more of these. Preferably, a resin composition containing at least one polymer selected from the group consisting of a polypropylene resin, a polyethylene resin, and an ethylene / propylene copolymer is used.

  In the present invention, the above-mentioned polyolefin resins can be used alone or in combination of at least two or more in a range not impairing the effects of the present invention.

  In the present invention, the method for producing a polyolefin resin is not particularly limited, and a known method can be used. For example, in a polypropylene resin, radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, Any method such as anionic polymerization or coordination polymerization using a metallocene catalyst can be used.

  When a polypropylene resin is used, the melt flow index (MI) measured in accordance with JIS-K7210 is excellent in terms of formation of sea-island structure with the biodegradable resin composition (A), crystallinity, moldability, and the like. 1-100 g / 10 minutes, preferably 2-80 g / 10 minutes, more preferably 4-60 g / 10 minutes. If it is this range, it will have suitable crystallinity, dimensional stability and moisture resistance, and the surface smoothness of resin layer (X) will become favorable. When MI is less than 1 g / 10 min, the melt viscosity is too high, the extrudability decreases, and the dispersibility of the biodegradable resin composition (A) tends to deteriorate. Moreover, when MI exceeds 100 g / 10min, the mechanical characteristics as a molded article may fall significantly.

  In addition, the isotactic index (II) of the polypropylene resin is preferably in the range of 92 to 99.8%, more preferably 94 to 99.5%. When II is less than 92%, problems such as an increase in heat shrinkage and deterioration of moisture resistance may occur. On the other hand, if II exceeds 99.8%, the processability during extrusion, spinning or stretching may be deteriorated.

  The intrinsic viscosity [η] of the polypropylene resin is 1.4 to 3.2 dl / g, preferably 1.6 to 2.4 dl / g. If [η] is smaller than 1.4 dl / g, the film is brittle, and if it exceeds 3.2 dl / g, the crystallinity may be lowered.

  In the present invention, the dispersant (C) is an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether from the viewpoint of dispersibility of the biodegradable resin composition (A). It is preferably a polyolefin resin-polystyrene resin block copolymer containing at least one functional group selected from the group consisting of a group, a hydroxyl group and an epoxy group. Among them, a block copolymer of a polyolefin resin-polystyrene resin containing an acid anhydride group and / or an epoxy group is more preferable, and a block copolymer of a polyolefin resin containing an acid anhydride group-polystyrene resin is preferred. Particularly preferred is a polymer. Further, a polymer having a mass average molecular weight of 1,000 to 300,000 is more preferable. Here, the mass average molecular weight is a mass average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The polyolefin resin-polystyrene resin block copolymer described above contains an olefin unit or a styrene vinyl unit, and preferably contains an olefin unit and a styrene vinyl unit as a main component. The total of these units is preferably 70% by mass or more, more preferably 90% by mass or more. Further, it may be a copolymer obtained by copolymerizing other vinyl units excluding olefin units and styrene vinyl units, preferably 30% by mass or less, more preferably 10% by mass or less.

  Further, in the above polyolefin resin-polystyrene resin block copolymer, when the polyolefin resin is represented by PO and the polystyrene resin is represented by PS, the composition of the block copolymer is a biodegradable resin composition. From the viewpoint of the dispersibility of (A), a triblock structure expressed as PS-PO-PS and PS-PO and a diblock structure are preferable, and a triblock structure expressed as PS-PO-PS. It is further preferable to take In the present invention, the ratio of the polystyrene resin in the polyolefin resin-polystyrene resin block copolymer is 5 to 5 in terms of dispersibility of the biodegradable resin composition (A). It is preferably 60% by mass, more preferably 10 to 40% by mass.

Here, the component amount (% by mass) of each component of the block copolymer of polyolefin resin-polystyrene resin was measured by a solution proton nuclear magnetic resonance method ( ¹ H-NMR), and the integrated intensity of each peak. It calculates from the composition ratio calculated | required more.

  In the present invention, specific examples of the raw material monomer for forming the olefinic vinyl unit are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1- Examples include octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and the like. Among these, ethylene, propylene, and 1-butene are preferably used. These may be used alone or in combination of two or more.

  In the present invention, specific examples of the raw material monomer for forming the styrene-based vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, Examples include 2,4-dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene, and the like. Among them, styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  In the present invention, specific examples of the raw material monomer that forms the epoxy group-containing vinyl unit that is a constituent unit of the polyolefin resin-polystyrene resin block copolymer include glycidyl (meth) acrylate, p- Glycidyl esters of unsaturated monocarboxylic acids such as glycidyl styryl carboxylate, monoglycidyl esters or polyglycidyl esters of unsaturated polycarboxylic acids such as maleic acid and itaconic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-4 -Unsaturated glycidyl ethers such as glycidyl ether. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used from the viewpoint of radical polymerizability. These can be used alone or in combination of two or more.

  In the present invention, specific examples of the raw material monomer that forms the acid anhydride group-containing vinyl-based unit that is a constituent unit of the polyolefin resin-polystyrene-based block copolymer include maleic anhydride and itaconic acid. An anhydride, citraconic acid anhydride, aconitic acid anhydride, etc. are mentioned, and maleic acid anhydride is preferably used. These may be used alone or in combination of two or more.

  In addition, examples of the raw material monomer that forms the unsaturated dicarboxylic acid unit serving as the carboxyl group-containing unit include maleic acid, maleic acid monoethyl ester, itaconic acid, and phthalic acid. Among these, maleic acid and itaconic acid are preferably used. Is done. These may be used alone or in combination of two or more.

  In the present invention, the melt flow index (MI) under the condition of 190 ° C. and 21.2N load of the polyolefin resin-polystyrene resin block copolymer is the dispersibility of the biodegradable resin composition (A). From the viewpoint, it is preferably 1 to 30 g / 10 minutes, more preferably 2 to 20 g / 10 minutes, and further preferably 3 to 16 g / 10 minutes. Here, the melt flow index (MI) is a value measured according to JIS-K7210.

  In the present invention, when the polyolefin resin-polystyrene resin block copolymer is an acid anhydride group-containing polyolefin resin-polystyrene resin block copolymer, the biodegradable resin composition (A) From the viewpoint of dispersibility, the acid anhydride group content is preferably 0.5 to 4% by mass, more preferably 0.8 to 3% by mass, and 1 to 2.5% by mass. More preferably it is. By using an acid anhydride group content of 0.5% by mass or more, the dispersibility of the biodegradable resin composition (A) becomes sufficient, and the acid anhydride group content is 4% by mass or less. Is preferably used because it is less likely to reduce moldability due to gelation or the like.

  In the present invention, the glass transition temperature of the above-mentioned polyolefin resin-polystyrene resin block copolymer is not particularly limited, but may be in the range of 30 to 100 ° C. from the viewpoint of excellent handling properties. Preferably, it is in the range of 40 to 70 ° 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. This glass transition temperature 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 olefinic vinyl units such as ethylene.

  In the present invention, the polyolefin resin-polystyrene resin block copolymer may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight material. The polymer usually 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 1,000 ppm or less (mass basis), 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 block copolymer of the above-described polyolefin resin-polystyrene resin is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization A known polymerization method such as emulsion polymerization can be used. When these methods are used, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used. These are impurities in the block copolymer of polyolefin resin-polystyrene resin finally obtained. May remain. 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 mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly 1% by mass or less, with respect to the finally obtained polymer. Most preferred.

  As a manufacturing method of the above-mentioned polyolefin resin-polystyrene resin block copolymer that satisfies the molecular weight, glass transition temperature, sulfur content, impurity amount, etc., for example, polyolefin resin-polystyrene resin After mixing a block copolymer with an acid anhydride and a reaction initiator such as an organic peroxide, a method of melt-kneading, or a polyolefin resin-polystyrene resin in an organic solvent such as benzene, toluene, xylene, etc. Examples include a method in which an acid anhydride and an organic peroxide are mixed with a block copolymer, heated, melted, and reacted. The organic peroxide here is a radical generator such as benzoyl peroxide, dicumyl peroxide, or t-butyl peroxide.

  Examples of the polyolefin resin-polystyrene resin block copolymer that can be used in the present invention include “Clayton FG” manufactured by Clayton, “Tuftec” manufactured by Asahi Kasei Chemicals, and “Dynalon” manufactured by JSR. it can.

  As the thermoplastic resin composition (E) forming the resin layer (Y), any of a polyolefin resin composition, a polyester resin composition, or a polyamide resin composition can be preferably used.

  The polyolefin resin of the polyolefin resin composition may be the same as or different from (B) contained in the resin layer (X), and is a mixture of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and the like. It can be selected from a copolymer or the like.

  As the carboxylic acid component constituting the polyester resin of the polyester resin composition, aromatic, aliphatic and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used. For example, aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, and aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, Dimer acids and the like, and their ester-forming derivatives can be used. As the glycol component of the polyester resin, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,4-butanediol, and the like can be used.

  Polyamide resins of the polyamide-based resin composition include polycapramide (nylon-6), poly-ω-aminoheptanoic acid (nylon-7), poly-ω-aminononanoic acid (nylon-9), polyundecanamide (nylon-11). ), Polylauryl lactam (nylon-12), polyethylene adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6) , Polyhexamethylene sebamide (nylon-6,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon- 10, 6), polydodecamethylene sebacamide (nylon-12, 10), or caprolacta / Lauryl lactam copolymer (nylon-6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), caprolactam / hexamethylene adipamide copolymer (nylon-6 / 6,6) ), Lauryl lactam / hexamethylene adipamide copolymer (nylon-12 / 6, 6), hexamethylene adipamide / hexamethylene sebamide copolymer (nylon-6, 6/6, 10), ethylene Adipamide / hexamethylene adipamide copolymer (nylon-2,6 / 6,6), caprolactam / hexamethylene adipamide / hexamethylene sebamide copolymer (nylon-6 / 6,6 / 6) 10), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexamethylene isophthalamide / terephthala Such as de copolymers. Of these polyamides, polyamides containing a caproamide component (for example, nylon-6, nylon-6, 12, nylon-6 / 12, nylon-6 / 6, 6, etc.) are preferred.

    The molded article of the present invention has a biodegradable resin composition (A) when the total weight of the biodegradable resin composition (A), the polyolefin resin composition (B) and the dispersant (C) is 100% by mass. ) Content (a) is in the range of 4 to 30% by mass, content (b) of the polyolefin-based resin composition (B) is in the range of 56 to 95% by mass, and the dispersant (C) is contained. The amount (c) is in the range of 0.1 to 20% by mass, and the content (a) of the biodegradable resin composition (A) and the content (b) of the polyolefin resin composition (B) It is important that the mass ratio (a / b) is in the range of 0.05 to 0.42.

  Within such a range, melt extrusion, stretching and the like in the film forming and spinning processes can be carried out stably.

  Below, the preferable aspect in the case of making the shape of the molded article of this invention into a film is described.

  The film of the present invention is preferably stretched in at least one direction. By stretching, the brittleness of the film is improved and the transparency is increased. Biaxial stretching is more preferable because it can provide a balanced film with little anisotropy of physical properties. In the case of biaxial stretching, a sequential biaxial stretching method in which stretching is performed in one direction and then further stretching in an orthogonal direction, or simultaneous biaxial stretching in which stretching is performed simultaneously in two orthogonal directions is used. It can be preferably used. As the film forming machine, either a tenter method or an inflation method can be used.

  As long as the effects of the present invention are not impaired, anti-blocking agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), lubricants (alkyl carboxylic acid amides, stearates, etc.), antistatic agents (alkyl sulfonates, alkyls) Fatty acid salts, alkyl fatty acid esters, etc.), plasticizers, colorants including dyes and pigments, nucleating agents, and the like can be added, but this may not be preferred when used as a vapor deposition film described below.

  An anti-blocking agent is a particle added to a resin component for the purpose of imparting irregularities to the film surface in order to suppress blocking between films and improve the handling properties of the film. Aggregated silica, colloidal silica, aluminosilicate, Inactive particles such as crosslinked PMMA, crosslinked polystyrene, and calcium carbonate can be used. Aggregated silica, colloidal silica, and aluminosilicate are particularly preferable.

  As the antistatic agent, a known cationic system, anionic system, zwitterionic system, or nonionic system can be used, and any of a method of coating on the film surface and a method of kneading the resin component can be used. However, in the case of kneading with a resin component, use of an ionic antistatic agent may cause undesirable decomposition during the kneading of the polylactic acid resin component, in which case a nonionic antistatic agent is preferably used. . Examples of the nonionic antistatic agent include polyhydric alcohols such as (poly) ethylene glycol, (poly) propylene glycol, glycerin and sorbit and / or fatty acid esters thereof.

  Any plasticizer may be used as long as it is added to the polylactic acid resin to induce a decrease in glass transition temperature and a decrease in rigidity. Examples of the plasticizer include ester derivatives and ether derivatives, and more specifically, ethers. Examples include ester derivatives, glycerin derivatives, phthalic acid derivatives, glycolic acid derivatives, citric acid derivatives, adipic acid derivatives, and epoxy plasticizers, but a plurality of these plasticizers may be blended and used.

  Although the manufacturing method of resin composition (D) which makes resin layer (X) is not specifically limited, For example, biodegradable resin composition (A), polyolefin resin composition (B), dispersing agent (C ) And, if necessary, other additives in advance, at a melting point or higher, uniformly melt-kneaded with a single-screw or twin-screw extruder, extruded into a strand, and then cut into pellets. A method of removing the solvent after mixing in the solution is preferably used.

  In the case of forming a film, a method of melt-extruding a pellet-shaped resin composition prepared in advance by the above-described method from a slit-shaped die from a single-screw or twin-screw extruder, a biodegradable resin composition (A), a polyolefin-based resin composition After pre-blending the resin composition (B), the dispersant (C) and other additives as required, the melt composition is melted and kneaded with a single-screw or twin-screw extruder directly above the melting point and directly from the slit-shaped die. Any technique of melt extrusion into a film can be used.

  As a method of compounding the resin layer (X) and the resin layer (Y), there is a method of laminating using a multi-manifold die, a field block, a static mixer, a pinol, etc. at the time of extrusion using two extruders. Preferably used. The layer structure is preferably resin layer (X) / resin layer (Y), resin layer (Y) / resin layer (X) / resin layer (Y), and the thickness of the resin layer (Y) is preferably 30 μm or less.

  The molten composition extruded into a film form from the die is brought into close contact with the casting drum by a method such as air knife or electrostatic application, and is cooled and solidified to form an unstretched film. Next, this unstretched film is stretched in one direction of the resin composition in the longitudinal direction or in the transverse direction, stretched in the longitudinal direction, then stretched in the transverse direction, stretched in the transverse direction, and then longitudinally A stretched film is obtained by stretching by a method of stretching, a method of stretching in the longitudinal direction and the transverse direction simultaneously, a method of performing stretching in the longitudinal direction and stretching in the width direction a plurality of times, or the like.

  The thickness of the film of the present invention is not particularly limited, but is preferably 1 to 1,000 μm, more preferably 3 to 300 μm, and more preferably 5 to 100 μm.

  The heat shrinkage of the film of the present invention is preferably 6% or less in the longitudinal direction and 4% or less in the width direction after heat treatment at 120 ° C. for 15 minutes. More preferably, the shrinkage rate in the longitudinal direction is 4% or less, the thermal shrinkage rate in the width direction is 2% or less, more preferably the shrinkage rate in the longitudinal direction is 2% or less, and the thermal shrinkage rate in the width direction is 1% or less. If the heat shrinkage ratio is within such a range, it is excellent in heat resistance and dimensional stability in the processing step, and can be suitably used for a packaging film or the like.

  Although the film of the present invention is excellent in water vapor barrier properties, it has low gas barrier properties such as oxygen, and therefore can be more suitably used by providing a barrier layer. The barrier layer can be provided by a technique such as coating, vapor deposition, or lamination, but vapor deposition is preferable because it does not depend on humidity and can exhibit barrier properties with a thin film.

  The vapor deposition layer is preferably made of any one of aluminum, aluminum oxide, silicon oxide, cerium oxide, calcium oxide, diamond-like carbon film, or a mixture thereof. In particular, aluminum deposition is more preferable because it is economical and has excellent gas barrier performance. In addition, as a method for producing a vapor deposition thin film, a physical vapor deposition method such as a vacuum vapor deposition method, an EB vapor deposition method, a sputtering method, and an ion plating method, and various chemical vapor deposition methods such as plasma CVD can be used. From the viewpoint, the vacuum deposition method is particularly preferably used.

When providing the vapor deposition layer, it is preferable to pre-treat the surface to be vapor-deposited by a method such as corona discharge treatment in order to improve the adhesion of the vapor deposition film. Processing strength when subjected to corona treatment is preferably 5~50W · min / ^{m 2,} more preferably 10~45W · min / ^{m 2.} Furthermore, you may perform surface treatments, such as a plasma processing, an alkali treatment, and an electron beam radiation process, as needed.

  If the surface to be deposited is smooth, the gas barrier properties are good, and therefore the resin layer (Y) is preferably designed to be smooth. In addition, the above-mentioned additives may bleed out on the film surface, resulting in a deposition defect, leading to a decrease in barrier properties, and caution is required.

  Moreover, higher gas barrier property can be obtained by using together with coating. If the primer agent is previously applied inline or off-line on the film, a vapor-deposited film having high adhesion can be obtained and effective in improving the gas barrier property. Moreover, if an overcoat agent is applied on a vapor deposition film, the defect of a vapor deposition film will be supplemented and it will lead to gas barrier property improvement.

  The use of the film of the present invention is not particularly limited, but when used as a packaging material, it is used for the purpose of preventing the drying of the package and the entry of moisture from the outside, such as food packaging, pharmaceutical packaging, Electronic component packaging, book packaging, and the like.

  Next, a preferable aspect in the case where the shape of the molded product of the present invention is a fiber will be described.

  The fiber of the present invention preferably takes the form of a nonwoven fabric from the viewpoint of mechanical strength. The single fiber fineness of the fiber is preferably 0.8 to 20 dtex, more preferably 0.9 to 12 dtex, and still more preferably 1.0 to 6 dtex. If the single fiber fineness is thinner than 0.8 dtex, the spinnability tends to deteriorate. Moreover, when the single fiber fineness exceeds 20 dtex, the fiber cannot be sufficiently cooled and the spinnability tends to deteriorate. In addition, the cross-sectional shape of the fiber is not limited at all, and a round shape, a hollow round shape, or an irregular shape such as an X shape or a Y shape is preferably used, but the round shape is most preferable from the viewpoint of easy production. It is preferable.

  The dry heat shrinkage ratio of the fiber of the present invention after heat treatment at 120 ° C. for 15 minutes is preferably 10% or less, more preferably 5% from the viewpoint of maintaining a mixed fiber state, that is, maintaining dimensional stability. Below, more preferably 3% or less. When the dry heat shrinkage rate is higher than 10%, wrinkles are likely to enter the non-woven fabric, which may cause a defect.

It is preferable that the fabric weight of the nonwoven fabric of this invention is 5-100 g / m < ² >. If the basis weight is less than 5 g / m ² , the strength of the nonwoven fabric tends to be insufficient. Further, when the basis weight exceeds 100 g / m ² , the strength is sufficient, but the cost per unit area is increased, and the flexibility tends to be lost. A preferable basis weight is 7 to 90 g / m ² , and a more preferable range is 10 to 70 g / m ² .

  Furthermore, the flexibility of the nonwoven fabric is preferably in the range of 10 to 150 mm as measured by a 45 ° cantilever method. When the measured value in the 45 ° cantilever method is less than 10 mm, practical mechanical strength may not be achieved. Moreover, since the flexibility is inferior when the measured value exceeds 150 mm, it is not preferable for hygiene materials. A more preferable range of flexibility (the range of the above measured values) is 15 to 120 mm, and more preferably 20 to 100 mm.

  Although the manufacturing method of the nonwoven fabric of this invention is not specifically limited, It is preferable to set it as a spun bond nonwoven fabric or a short fiber nonwoven fabric from the point that a manufacturing method is simple and is excellent in production capacity. A particularly preferable production method is a spunbonded nonwoven fabric from the viewpoint of mechanical strength.

  The spunbonded nonwoven fabric used in the present invention is not particularly limited, but after extruding a molten polymer from a nozzle and sucking and stretching it with a high-speed suction gas, the fibers are collected on a moving conveyor. A web manufactured by a so-called spunbond method, which is a sheet integrated by continuous thermal bonding, entanglement, or the like, is preferable.

  In addition, the short fibers can be subjected to a predetermined crimping process by a stuffing box method or an indentation heating gear method before cutting. In the case of producing a short fiber nonwoven fabric by a dry method, the number of crimps of the short fiber is preferably 5 to 50/25 mm, more preferably 10 to 30/25 mm, and the cut length of the short fiber is 10 -80 mm is preferable, More preferably, it is 20-60 mm. When the number of crimps is less than 5/25 mm, unopened fibers are likely to occur during opening, which is an undesirable direction. On the other hand, if the number of crimps exceeds 50/25 mm, a uniform fiber opening may not be obtained, which is an undesirable direction.

  The nonwoven fabric of the present invention is preferably partially thermally bonded and integrated. The area for thermal bonding is preferably 5 to 50% of the total area of the nonwoven fabric. More preferably, it is 8-45%, More preferably, it is 10-30%. When the area of thermal bonding is less than 5%, the strength of the nonwoven fabric tends to be weak, which is an undesirable direction. Moreover, when the area of heat bonding exceeds 50%, although it is excellent in the mechanical strength of a nonwoven fabric, it exists in the tendency for a softness | flexibility to be impaired.

  The method of partial thermal bonding is not particularly limited, but bonding with a pair of hot embossing rolls or bonding with an ultrasonic oscillator and an embossing roll is a preferred method, but in terms of strength, a pair of hot embossing rolls. Adhesion by is more preferable. The temperature of heat bonding by the hot embossing roll is preferably 5 to 50 ° C., more preferably 10 to 40 ° C. lower than the melting point of the resin existing on the fiber surface. When the temperature of heat bonding by the hot embossing roll is lower than the melting point of the resin existing on the fiber surface by less than 5 ° C., the resin is melted severely, the sheet is taken on the embossing roll, roll contamination occurs, Not only is it stiff, but also roll winding often occurs, making stable production impossible. Further, when the temperature is lower than the melting point of the resin existing on the fiber surface by more than 50 ° C., the resin is insufficiently fused and tends to be weak in physical properties.

  The nonwoven fabric of the present invention preferably has a water pressure resistance of 60 to 200 mmAq. When the water pressure resistance is less than 60 mmAq, it is difficult to use in applications requiring water repellency and water resistance. In addition, when the water pressure resistance exceeds 200 mmAq, the fabric weight of the nonwoven fabric must be increased more than necessary, and the amount of water repellent contained in the nonwoven fabric must be increased more than necessary, which not only increases the cost but also increases flexibility. Sex is easily lost. A preferable water pressure resistance is 70 to 180 mmAq, more preferably 80 to 170 mmAq.

  In the nonwoven fabric of the present invention, the water repellent preferably comprises at least one of a fluorine compound, a polyolefin compound, and a silicone compound. The most preferable water repellent is a fluorine-based compound from the viewpoint of excellent water repellency. The amount of the water repellent is preferably in the range of 0.05 to 5% by mass with respect to the nonwoven fabric. When the applied amount of the water repellent is less than 0.05% by mass with respect to the nonwoven fabric, the water repellency and water resistance tend to be insufficient, which is not preferable. When the application amount of the water repellent exceeds 5% by mass with respect to the nonwoven fabric, not only the cost becomes high, but the breathability of the nonwoven fabric may be lost. The method for incorporating the water repellent into the nonwoven fabric is not limited at all. For example, air doctor coat, blade coat, rod coat, knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss roll coat, cast coat, spray coat, curtain coat, calendar coat, foam coat Alternatively, an extrusion coating method is preferable. As a particularly preferred method, an impregnated coating method in which a nonwoven fabric is impregnated into an emulsified water repellent and a predetermined amount of water repellent is applied, or a kiss that transfers the emulsified water repellent to a non-woven fabric with a predetermined amount of kiss roll. Roll coating method. The temperature at which the nonwoven fabric provided with the water repellent is dried is not particularly limited, but is preferably 60 to 160 ° C. in order to improve water repellency and water resistance. When the drying temperature is lower than 60 ° C., the water repellency may be insufficient, which is not preferable. On the other hand, when the drying temperature exceeds 160 ° C., the melting point and softening point of the biodegradable resin composition (A) are low, and the nonwoven fabric tends to shrink and deteriorate, which is not preferable. A more preferable drying temperature is 70 to 150 ° C, and more preferably 80 to 130 ° C. Further, the drying time is preferably in the range of 1 to 600 seconds. When the drying time is shorter than 1 second, the drying is insufficient, and the water repellency may be insufficient. Further, when the drying time exceeds 600 seconds, not only the productivity is lowered, but also the nonwoven fabric tends to shrink or deteriorate, which is not preferable.

  The nonwoven fabric of the present invention can be used for any application, but is preferably used for sanitary materials because of its excellent mechanical strength and flexibility and good water resistance. Specific examples of sanitary materials here include disposable clothing that can be used only once, such as protective clothing and underwear, sanitary products such as sanitary napkins and panty shields, adult diapers, baby diapers, and incontinence. Disposable diapers such as a person's pad, bed sheets such as sheets, bed covers and pillow covers, and kitchen utensils such as an apron and gloves, but are not particularly limited thereto.

  Hereinafter, the present invention will be described based on examples and comparative examples.

  In addition, about the measuring method etc., it implemented by the method as described below.

[Melt Flow Index (MI)]
According to JIS-K-7210 (1999), the measurement was performed under the conditions of 230 ° C. and a load of 2.16 kg.

[Isotactic index (II)]
The sample is dried under reduced pressure at 130 ° C. for 2 hours, from which a sample of mass W (mg) is taken, placed in a Soxhlet extractor and extracted with boiling n-heptane for 12 hours. Next, this sample is taken out, washed sufficiently with acetone, dried under reduced pressure at 130 ° C. for 6 hours, then cooled to room temperature, measured for mass W ′ (mg), and determined by the following formula.

II (%) = (W ′ / W) × 100
[Intrinsic viscosity [η]]
According to ASTM D 1601 (1999), 0.1 g of a sample was completely dissolved in 100 ml of tetralin at 135 ° C., and this solution was measured with a viscometer in a thermostatic bath at 135 ° C. Ask. The unit is dl / g.

[Η] = S / 0.1 × (1 + 0.22 × S)
[Amount of copolymerization component]
Using JNM-30AL400 manufactured by JEOL, the spectrum was measured by a solution proton nuclear magnetic resonance method ( ¹ H-NMR), and the mass ratio was calculated from the composition ratio determined from the integrated intensity of each peak.

  Measurement conditions were as follows: Desolved solvent in deuterated chloroform at room temperature, sample concentration 20 mg / mL, pulse width 11 μs / 45 °, pulse turn-back time 9 seconds, integration number 256 times, 23 ° C. It was measured.

[Dispersion diameter]
An ultrathin section is prepared using a microtome so that the cross section of the resin composition (D) becomes the sample surface, and this thin film section is accelerated using a transmission electron microscope (H-7100FA model manufactured by Hitachi High-Technologies Corporation). A cross-sectional photograph was taken at a voltage of 100 kv and a magnification of 5,000. For 10 arbitrary dispersed domains observed in the photograph, the arithmetic average value of the minor axis and the major axis was taken as the particle size of the particle, and the arithmetic of the particle size The average value was taken as the dispersion diameter.

[Film thickness]
According to JIS-B-7509 (1955), it measured using the dial gauge type thickness meter.

[Heat shrinkage]
According to JIS-Z-1712 (1997), the shrinkage ratio after heat-treating at 120 ° C. for 15 minutes was determined.

[Optical density (OD)]
Using an optical densitometer (TR927 manufactured by Gretag Macbeth Co., Ltd.), it was calculated from the following formula.

A projection light I ₀ incident to the sample, the ratio of transmitted light I passing through the sample, expressed in common logarithm of the reciprocal of transmittance.

OD = log (I ₀ / I)
[Water vapor permeability]
Using a water vapor transmission rate measuring device (model name, “Permatran” (registered trademark) W3 / 31) manufactured by MOCON, USA, under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, JIS It measured based on B method (infrared sensor method) as described in K7129 (2000). Moreover, the measurement was performed twice and it calculated | required from the average of two measured values. Evaluation was performed about the raw film and the vapor deposition film.

[Oxygen permeability]
Using an oxygen transmission rate measuring device (model name, “Oxytran” (registered trademark) (“OXTRAN” 2/20)) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 0% RH , Measured according to the method B (isobaric method) described in JIS K7126 (2000). Moreover, the measurement was performed twice and it calculated | required from the average of two measured values. Evaluation was performed about the vapor deposition film.

[Single yarn fineness]
Ten small sample samples are taken at random from the nonwoven fabric, photographed at 500 to 3,000 times with a scanning electron microscope, the diameter of 100 fibers, 10 from each sample, is measured, and the average value is obtained. From this, the fiber diameter was calculated, and this was corrected by the polymer density to calculate the fineness.

[Unit weight]
In accordance with 4.2 of JIS-L1906 (1994), three samples of 50 cm in the vertical direction x 50 cm in the horizontal direction were collected, the mass of each sample was measured, and the average value obtained was converted per unit area. The basis weight (g / m ² ) of the nonwoven fabric was used.

[Tensile strength]
In accordance with JIS-L1906 (1994) 4.3.1, three points were measured in the longitudinal and lateral directions of the sheet under the conditions of a sample size of 5 × 30 cm, a gripping interval of 20 cm, and a tensile speed of 10 cm / min. Was converted to a strength per 100 g / m ² , and those of 30 N / 5 cm or more in both the longitudinal direction and the transverse direction were accepted (◯), and the others were judged as unacceptable (x).

[Dry heat shrinkage]
A test piece having a width of 5 cm and a length of 30 cm was cut out from the non-woven fabric, and the dry heat shrinkage rate when held in a hot air oven at a temperature of 120 ° C. for 15 minutes was determined by the following equation.

Dry heat shrinkage of nonwoven fabric (%) = {(A0−A1) / A0} × 100
A0: Original length in the longitudinal direction (cm)
A1: Longitudinal dimension after heat treatment (cm)
[Water pressure (water repellency)]
According to 6.1 water resistance test (hydrostatic pressure method) A method (low water pressure method) of JIS-L1092 (1977), 5 points were measured at a sample size of 15 × 15 cm, and the average value was regarded as the water resistance of the nonwoven fabric.

  Hereinafter, the present invention will be described by way of examples.

Example 1
Polypropylene (1) (manufactured by Sumitomo Chemical Co., Ltd. “Nobrene” WF836DG3 MI: 7 g / 10 min, II: 98.8%, intrinsic viscosity: 1.80 dl / g) 80 parts by mass, polylactic acid (1) (manufactured by NatureWorks, molecular weight of about 200,000) ) 20 parts by mass, maleic anhydride-modified SEBS (manufactured by Kraton "Clayton" FG1924 maleic anhydride-modified styrene-ethylene / butylene-styrene copolymer, styrene content 13% by mass, maleic acid modification rate 1.0% by mass) Mixing 10 parts by mass, using a 30mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel), melt kneading under conditions of a cylinder temperature of 210 ° C and a rotation speed of 200rpm, and discharging a strand with a diameter of about 3mm into water The resin composition (D-1) pellets were obtained by solidification and cutting with a length of 4 mm.

  (D-1) to be the resin layer (X) was supplied to the single screw extruder-1, and polypropylene (1) to be the resin layer (Y) was supplied to the single screw extruder-2. Extruded at 220 ° C in a sheet form with a multilayer die, wound around a drum at a temperature of 50 ° C and cooled into a sheet form so as to have a three-layer structure of resin layer (Y) / resin layer (X) / resin layer (Y) Solidified. The film is preheated at 135 ° C. and stretched at 135 ° C., stretched 5 times in the longitudinal direction with a roll, immediately cooled to room temperature, stretched 6 times in the width direction at a temperature of preheating 165 ° C. and stretched at 160 ° C. Next, heat treatment was performed at a temperature of 160 ° C. while giving 5% relaxation in the width direction to obtain a biaxially stretched film. The thickness of the obtained film was 15.0 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 14.6 / 1.

The obtained film was wound by applying a corona discharge treatment at 30 W · min / m ² while maintaining the film temperature at 60 ° C. in an atmosphere of a mixed gas of nitrogen and carbon dioxide (carbon dioxide concentration ratio: 15 vol%). . It set in the vacuum evaporation apparatus which equipped the film travel apparatus, and after making it the high pressure reduction state of 1.00 * 10 ^<-2 > Pa, it was made to travel through a 20 degreeC cooling metal drum. At this time, the aluminum metal was heated and evaporated to form a deposited thin film layer. After vapor deposition, the inside of the vacuum vapor deposition apparatus was returned to normal pressure, and the wound film was rolled back and aged at a temperature of 40 ° C. for 2 days to obtain a vapor deposited film. The vapor deposition thickness was controlled so that the optical density of the vapor deposition film was 2.5.

(Example 2)
Similar to Example 1, except that polypropylene (2) (“Noblen” FS2016 MI: 2.1 g / 10 min II: 97%, intrinsic viscosity 2.1 dl / g, manufactured by Sumitomo Chemical) was used instead of polypropylene (1). Melt kneading was performed with a twin-screw extruder to obtain resin composition (D-2) pellets. Example 1 except that (D-2) serving as the resin layer (X) was supplied to the single screw extruder-1 and polypropylene (2) serving as the resin layer (Y) was supplied to the single screw extruder-2. Similarly, a three-layer laminated biaxially stretched film was produced. The thickness of the obtained film was 14.6 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 13.9 / 1. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

(Example 3)
Resin composition was melt kneaded with a twin-screw extruder in the same manner as in Example 1 except that polypropylene (3) (“Prime Polypro” J160G MI: 15 g / 10 min manufactured by Prime Polymer) was used instead of polypropylene (1). (D-3) A pellet was obtained. (D-3) to be the resin layer (X) is supplied to the single screw extruder-1, and polypropylene (3) to be the resin layer (Y) is supplied to the single screw extruder-2, and the drawing conditions are preheated. 135 ° C, stretching 135 ° C, stretched 3.5 times in the longitudinal direction with a roll, immediately cooled to room temperature, preheated to a tenter at a temperature of 165 ° C and stretched 160 ° C, stretched 4.2 times in the width direction, and then width While giving a relaxation of 5% in the direction, heat treatment was performed at a temperature of 160 ° C. to obtain a biaxially stretched film. The thickness of the obtained film was 16.6 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 13.9 / 1. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

Example 4
A resin composition (D-4) was obtained by melt-kneading with a twin-screw extruder in the same manner as in Example 1 except that imine group-modified SEBS (“Toughtech” M1943 manufactured by Asahi Kasei Chemicals) was used instead of maleic anhydride-modified SEBS. The pellet (D-4) to be the resin layer (X) was supplied to the single-screw extruder-1, and thereafter a three-layer laminated biaxially stretched film was produced in the same manner as in Example 1. The thickness of the film was 15.3 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 14.2 / 1. In the same manner as above, vapor deposition was performed to obtain a vapor deposition film.

(Example 5)
Resin composition (D-5) pellets were melt kneaded with a twin screw extruder in the same manner as in Example 1 except that amino group-modified SEBS (“Dynalon” 8630P manufactured by JSR) was used instead of maleic anhydride-modified SEBS. Got. (D-5) to be the resin layer (X) was supplied to the single screw extruder-1, and thereafter a three-layer laminated biaxially stretched film was produced in the same manner as in Example 1. The thickness of the obtained film was 15.0 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 14.1 / 1. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

(Example 6)
Resin was melt kneaded with a twin screw extruder in the same manner as in Example 1 except that ethylene-vinyl acetate copolymer resin (“Evaflex” EV450 manufactured by Mitsui DuPont Chemical) was used instead of maleic anhydride-modified SEBS. Composition (D-6) pellets were obtained. (D-6) used as resin layer (X) was supplied to the single screw extruder-1, and the three-layer lamination biaxially stretched film was produced similarly to Example 1 after that. The thickness of the obtained film was 14.7 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 16.0 / 1. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

( Reference Example 7)
Biaxial as in Example 1, except that the raw material blending ratio was 70 parts by mass of polypropylene (1), 30 parts by mass of polylactic acid (1) (molecular weight of about 200,000 manufactured by NatureWorks), and 10 parts by mass of maleic anhydride-modified SEBS. Melt-kneading was performed with an extruder to obtain resin composition (D-7) pellets. (D-7) to be the resin layer (X) was supplied to the single screw extruder-1, and thereafter a three-layer laminated biaxially stretched film was produced in the same manner as in Example 1. The thickness of the obtained film was 15.0 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 15.2 / 1. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

(Example 8)
In the single screw extruder-2, ethylene propylene random copolymer polypropylene (EPC) containing 1% by mass of ethylene to be the resin layer (Y) (“Noblen” FSX41E2, manufactured by Sumitomo Chemical Co., Ltd., II: 93%, limiting viscosity 1.8 dl) Thereafter, a three-layer laminated biaxially stretched film was produced in the same manner as in Example 1 except that / g) was supplied. The thickness of the obtained film was 15.1 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 15.1 / 1. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

(Comparative Example 1)
Without using the single screw extruder-2, the resin composition (D-1) was supplied to the single screw extruder-1, and a film consisting only of the resin layer (X) was formed. The film forming conditions were the same as in Example 1, and the thickness of the obtained biaxially stretched film was 13.8 μm. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

(Comparative Example 2)
Biaxial as in Example 1, except that the raw material blending ratio was 60 parts by mass of polypropylene (1), 40 parts by mass of polylactic acid (1) (molecular weight of about 200,000 manufactured by NatureWorks), and 10 parts by mass of maleic anhydride-modified SEBS. Melt-kneading was performed with an extruder to obtain resin composition (D-8) pellets. (D-8) to be the resin layer (X) was supplied to the single screw extruder-1, and thereafter a three-layer laminated biaxially stretched film was produced in the same manner as in Example 1. The thickness of the obtained film was 14.7 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 11.2 / 1. Vapor deposition was performed in the same manner as in Example 1 to obtain a vapor deposition film.

(Comparative Example 3)
Biaxial as in Example 1 except that the raw material blending ratio was 30 parts by mass of polypropylene (1), 70 parts by mass of polylactic acid (1) (molecular weight of about 200,000 manufactured by NatureWorks), and 10 parts by mass of maleic anhydride-modified SEBS. Melt kneading was performed with an extruder to obtain resin composition (D-9) pellets. (D-9) to be the resin layer (X) was supplied to the single screw extruder-1 and three-layer lamination was attempted in the same manner as in Example 1, but lamination disorder occurred and stretching was impossible.

(Comparative Example 4)
The raw material blending ratio was set to 70 parts by mass of polypropylene (1) and 30 parts by mass of polylactic acid (1) (molecular weight of about 200,000 manufactured by NatureWorks), and melt kneading was performed to obtain resin composition (D-10) pellets. (D-10) used as the resin layer (X) was supplied to the single screw extruder-1, and the three-layer lamination biaxially stretched film was produced similarly to Example 1 after that. The thickness of the obtained film was 14.7 μm, and the thickness constitution of the film was resin layer (Y) / resin layer (X) / resin layer (Y) = 1 / 11.2 / 1. Vapor deposition was performed in the same manner as in Example 1 to obtain a vapor deposition film.

(Comparative Example 5)
Without using the single screw extruder-2, polypropylene (1) was supplied to the single screw extruder-1, and a film consisting only of the resin layer (X) was formed. The film forming conditions were the same as in Example 1, and the thickness of the obtained biaxially stretched film was 15.0 μm. The film was deposited in the same manner as in Example 1 to obtain a deposited film.

  Tables 1 and 2 show the compositions and evaluation results of the obtained films.

Example 9
(D-3) produced in Example 3 was supplied as a resin layer (X) to the single screw extruder-1, and polypropylene (3) serving as the resin layer (Y) was supplied to the single screw extruder-2. . Using a core-sheath type spinneret, core layer: resin layer (X), sheath layer: resin layer (Y), core-sheath ratio 5/1, spinning from the pores at a base temperature of 220 ° C., spinning by ejector A web obtained by spinning at a speed of 4,000 m / min and being collected on a moving net conveyor is an embossing roll and a flat roll having a convex area of 15%, a temperature of 140 ° C. and a pressure of 50 kg / cm. To produce a spunbonded nonwoven fabric having a single yarn fineness of 1.5 dtex and a basis weight of 20 g / m ² .

(Example 10)
A spunbonded nonwoven fabric was produced under the same conditions as in Example 9 except that (D-4) produced in Example 4 was used as the resin layer (X). The single yarn fineness was 1.8 dtex.

(Comparative Example 6)
A spunbond nonwoven fabric was prepared in the same manner as in Example 9 except that the resin composition (D-3) was supplied to the single screw extruder-1 without using the single screw extruder-2 and only the resin layer (X) was used. did. The single yarn fineness was 1.7 dtex.

(Comparative Example 7)
Except for using (D-9) produced in Comparative Example 3 as the resin layer (X), an attempt was made to produce a spunbonded nonwoven fabric under the same conditions as in Example 9, but the spinning was not stable, and thus production was impossible. Met.

  As shown in Tables 1 to 4, the molded article of the present invention has excellent moisture resistance and dimensional stability, and is suitable as a general industrial or packaging material film, a non-woven fabric for food, sanitary material, or industrial material. Can be used.

Claims (13)

A molded product having a layer structure in which a resin layer (X) made of a resin composition (D) and a resin layer (Y) made of a thermoplastic resin composition (E) are laminated, and the resin composition (D ) Includes a biodegradable resin composition (A), a polyolefin resin composition (B), and a dispersant (C), and the biodegradable resin composition (A) is an polyolefin component (B). ) average dispersed diameter is 1nm or more in, have a dispersed island structure below 1,000 nm, the total weight of the biodegradable resin composition (a), the polyolefin resin composition (B) and dispersing agent (C) Is 100% by mass,
(1) The content (a) of the biodegradable resin composition (A) is in the range of 4 to 30% by mass,
(2) The content (b) of the polyolefin resin composition (B) is in the range of 56 to 95% by mass,
(3) The content (c) of the dispersant (C) is in the range of 0.1 to 20% by mass,
And,
(4) The mass ratio (a / b) of the content (a) of the biodegradable resin composition (A) and the content (b) of the polyolefin resin composition (B) is 0.05 to 0.42. Molded products in the range of The molded article according to claim 1, wherein the biodegradable resin composition (A) comprises a polyester resin composition obtained by polymerizing a lactic acid monomer. The molded article according to claim 1 or 2, wherein the polyolefin-based resin composition (B) contains at least one polymer selected from the group consisting of a polypropylene resin, a polyethylene resin, and an ethylene / propylene copolymer resin. The dispersant (C) has at least one functional group selected from the group consisting of an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group. The molded article according to any one of claims 1 to 3, which is a block copolymer of a polyolefin-based resin-polystyrene-based resin. The molded article according to any one of claims 1 to 4, wherein the thermoplastic resin composition (E) is any one of a polyester resin composition, a polyolefin resin composition, and a polyamide resin composition. The molded product according to any one of claims 1 to 5, wherein the shape is a film. The molded article according to claim 6, which is stretched in at least one direction. The molded article according to claim 6 or 7, wherein the heat shrinkage in the longitudinal direction is 6% or less and the heat shrinkage in the width direction is 4% or less after heat treatment at 120 ° C for 15 minutes. The molded article according to any one of claims 6 to 8, which is used as a packaging film. The molded product according to any one of claims 1 to 5, wherein the shape is a fiber. The molded article according to claim 10, wherein the single yarn fineness is 0.8 to 20 dtex. The molded article according to claim 10 or 11, wherein the dry heat shrinkage after heat treatment at 120 ° C for 15 minutes is 0 to 10%. The molded article according to any one of claims 10 to 12, which is used as a nonwoven fabric.