JP6668590B2 - Polyarylene sulfide resin particle dispersion, thermoplastic resin composition, molded article, sheet or sheet, and method for producing them - Google Patents

Description

  The present invention relates to a polyarylene sulfide resin particle dispersion containing fine particles of a polyarylene sulfide resin (PAS resin) typified by a polyphenylene sulfide resin (PPS resin) in a thermoplastic elastomer as a dispersion and a method for producing the same.

  The present invention also relates to a thermoplastic resin composition containing the polyarylene sulfide resin particle dispersion and a thermoplastic resin, and a molded article, particularly a sheet or a film, comprising the thermoplastic resin composition and a method for producing the same.

  More specifically, the present invention relates to a polyarylene sulfide resin particle dispersion containing fine particles made of a polyarylene sulfide resin having heat resistance, and a thermoplastic resin composition having excellent heat resistance obtained by mixing the dispersion with a thermoplastic resin. , A molded article having excellent heat resistance, particularly a sheet or film, and a microporous sheet or film obtained by making the sheet or film porous, a non-aqueous electrolyte secondary battery comprising the thermoplastic resin The present invention relates to a microporous sheet or film for a separator and a method for producing the same.

  With the development of cordless and portable electronic devices, non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries having high electromotive force and low self-discharge have attracted attention as power sources for driving these devices. In recent years, in particular, with the progress of higher energy densities, adoption not only for conventional electronic devices but also for automobiles has rapidly increased, and further safety is required.

   In non-aqueous electrolyte secondary batteries, a separator is interposed between the positive electrode and the negative electrode to prevent a short circuit between the two electrodes.However, as such a separator, a large number of micropores are formed to ensure the permeability of ions between the two electrodes. The used microporous sheet or film (hereinafter referred to as “microporous membrane”) is used. At present, polyolefin microporous membranes have not only excellent mechanical properties but also a polyolefin microporous membrane from the viewpoint of having a “shutdown function” in which the pores of the microporous membrane are closed and the current is shut off when the battery temperature rises. A porous membrane is used. However, when the non-aqueous electrolyte secondary battery starts thermal runaway and continues to rise in temperature, the separator composed of the above-mentioned microporous polyolefin membrane causes thermal shrinkage, breaks the film, and causes a “melt down” in which both electrodes are short-circuited (short-circuited). There is a problem to cause.

  For this reason, the microporous membrane is required to have a shutdown function and "heat-shrink resistance" to prevent meltdown. However, since the shutdown function uses blockage of pores due to melting of polyolefin, its operation principle is The property is inconsistent with shrinkability.

  Therefore, in order to improve the heat shrink resistance and to achieve the shutdown function at the same time, spherical particles having a diameter of 1 to 10 μm made of polybutylene terephthalate (PBT) having a high melting point are dispersed in a polyolefin matrix. A microporous membrane has been proposed (see Patent Document 1). However, the microporous membrane has insufficient heat shrink resistance, and further improvement has been required.

JP 2004-149637 A

  In view of the above circumstances, the problem to be solved by the present invention is to mix with thermoplastic resins such as olefin-based resins and maintain various properties such as mechanical strength of the thermoplastic resin while maintaining heat resistance. It is an object of the present invention to provide a molded article such as a sheet or a film, and a material capable of providing the molded article, and a method for producing the same. More specifically, a microporous film which can be used as a separator for a non-aqueous electrolyte secondary battery having excellent heat shrink resistance when blended with an olefin resin, and polyarylene sulfide resin particles capable of providing the microporous film An object of the present invention is to provide a dispersion, a thermoplastic resin composition containing the dispersion, and a method for producing the same.

  Means for Solving the Problems The present inventors have made intensive efforts to solve the above problems, and as a result, a polyarylene sulfide resin (A) having a specific melt viscosity and a polyolefin (B1) having a functional group or a polyolefin resin containing a polyolefin (B1) having a functional group. Polyarylene sulfide resin particles in which the polyolefin (B1) or the polyolefin resin composition (B) is used as a matrix and the PAS resin is finely dispersed as extremely fine particles by melt-kneading the composition (B) at a specific ratio. Finding to form a dispersion, further obtained by blending the obtained polyarylene sulfide resin particle dispersion with a thermoplastic resin, to find a molded article excellent in mechanical properties, particularly to provide a sheet or film, The present invention has been completed. Further, they found that a microporous membrane containing a polyolefin as a matrix and containing the polyarylene sulfide resin particle dispersion was excellent in mechanical properties and excellent in affinity with an organic polar solvent, and was used as a separator for a non-aqueous electrolyte secondary battery. The present inventors have found that the present invention can be used, and have completed the present invention.

That is, according to the present invention, the particles composed of the polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300 ° C. in the range of 100 to 2000 (Pa · s) are contained in the polyolefin (B1) having a functional group or A polyarylene sulfide resin particle dispersion dispersed in a polyolefin resin composition (B) containing a group-containing polyolefin (B1),
The particles relate to a polyarylene sulfide resin particle dispersion, in which the proportion of particles having a particle diameter of 100 nm or less in all particles is 10% or more in fractions.

Further, the present invention relates to a method for producing a polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300 ° C. in the range of 100 to 2000 (Pa · s) in a polyolefin (B1) having a functional group or a functional group. The particles are dispersed in a polyolefin resin composition (B) containing a polyolefin having a group (B1), and the ratio of the particles having a particle size of 100 nm or less to all the particles is 10% or more as a fraction. A method for producing a polyarylene sulfide resin particle dispersion,
Melting and kneading the polyarylene sulfide resin (A) in a range of 70 to 50 parts by mass and the polyolefin resin composition (B) in a range of 30 to 50 parts by mass at a temperature higher than the melting point of the polyarylene sulfide resin. And a method for producing a polyarylene sulfide resin particle dispersion.

Further, the present invention provides a method wherein the particles comprising the polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300 ° C. in the range of 100 to 2000 (Pa · s) are a polyolefin (B1) having a functional group or a functional group. A thermoplastic resin composition dispersed in a polyolefin resin composition (B) containing a polyolefin (B1) having the formula (I) and a thermoplastic resin (C) having a melting point lower than that of the polyarylene sulfide resin. ,
The above-mentioned particles relate to a thermoplastic resin composition, wherein the proportion of particles having a particle size of 100 nm or less in all particles is 20% or more in fractions.

In addition, the present invention provides the polyarylene sulfide resin particle dispersion in an amount of 10 to 70 parts by mass and the thermoplastic resin (C) in an amount of 30 to 90 parts by mass lower than the melting point of the polyarylene sulfide resin and the polyolefin. Melt kneading in a temperature range higher than the melting point of any of the resin composition (B) and the thermoplastic resin (C),
Particles comprising a polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300 ° C. in the range of 100 to 2000 (Pa · s) are a polyolefin having a functional group (B1) or a polyolefin having a functional group (B1). Is dispersed in a resin composition containing a thermoplastic resin (C) having a lower melting point than the polyolefin resin composition (B) containing polyolefin and the polyarylene sulfide resin,
Further, the present invention relates to a method for producing a thermoplastic resin composition in which the ratio of particles having a particle size of 100 nm or less to all particles is 20% or more in fractions.

  The present invention also relates to a molded article obtained by melt-molding the thermoplastic resin composition described above, and further relates to a sheet or film.

In addition, the present invention provides the polyarylene sulfide resin particle dispersion in an amount of 10 to 70 parts by mass and the thermoplastic resin (C) in an amount of 30 to 90 parts by mass lower than the melting point of the polyarylene sulfide resin and the polyolefin. A step (1) of melt-kneading the resin composition (B) and the thermoplastic resin (C) in a temperature range higher than the melting point of any one of the resin composition (B) and the thermoplastic resin (C) to obtain a thermoplastic resin composition;
Sheeting the thermoplastic resin composition heated to a temperature lower than the melting point of the polyarylene sulfide resin and higher than the melting point of any of the polyolefin resin composition (B) and the thermoplastic resin (C); The film is formed, and the particles comprising the polyarylene sulfide resin (A) are dispersed in a resin composition containing the polyolefin resin composition (B) and the thermoplastic resin (C), and the particles are: (2) obtaining a sheet or film in which the proportion of particles having a particle size of 100 nm or less in all particles is 10% or more in fractions.

Further, the present invention is obtained by forming a porous sheet or film obtained by melt-molding the thermoplastic resin composition,
Particles made of the polyarylene sulfide resin (A) are dispersed in a resin composition containing the polyolefin resin composition (B) and the thermoplastic resin (C), and the particles are contained in all particles. The present invention relates to a microporous sheet or film in which the proportion of particles having a particle size of 100 nm or less occupies 10% or more in fractions.

  Further, in the present invention, in the step (1), in addition to the polyarylene sulfide resin particle dispersion and the thermoplastic resin (C), a pore forming agent (D) or a β crystal nucleating agent (E) is further kneaded, A method for producing a microporous sheet or film, further comprising, after the steps (1) and (2), a step (3) of making the sheet or film obtained in the step (2) porous. , Concerning.

  According to the present invention, while being mixed with a thermoplastic resin such as an olefin-based resin, while maintaining various properties such as mechanical strength of the thermoplastic resin, molding of a sheet or a film having excellent heat resistance. Article, a material capable of providing the molded article, and a method for producing the same. More specifically, a microporous film which can be used as a separator for a non-aqueous electrolyte secondary battery having excellent heat shrink resistance when blended with an olefin resin, and polyarylene sulfide resin particles capable of providing the microporous film A dispersion, a thermoplastic resin composition containing the dispersion, and a method for producing the same can be provided.

3 is an image of the PPS particle dispersion obtained in Example 1 taken with a SEM (3000 times magnification). 4 is a graph showing the particle size distribution of PPS particles contained in the PPS particle dispersion obtained in Example 1.

-Polyarylene sulfide resin particle dispersion The polyarylene sulfide resin particle dispersion of the present invention comprises a polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300 ° C and in the range of 100 to 2000 (Pa · s). A polyarylene sulfide resin particle dispersion in which particles are dispersed in a polyolefin having a functional group (B1) or a polyolefin resin composition (B) containing the polyolefin having a functional group (B1),
The particles are characterized in that the proportion of particles having a particle size of 100 nm or less in all the particles is 10% or more in fractions.

..Polyarylene sulfide resin (A)
The polyarylene sulfide resin (A) used in the present invention has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit, and specifically has the following formula (1)

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). It is a resin having a structural part as a repeating unit.

Here, in the structural site represented by the formula (1), particularly, R ¹ and R ² in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. And those bonded at the para position represented by the following formula (2) are preferred.

Among these, it is particularly preferable that the bond of the sulfur atom to the aromatic ring in the repeating unit be a structure bonded at the para position represented by the structural formula (2). Preferred in terms of surface.

  Further, the polyarylene sulfide resin includes not only the structural part represented by the formula (1) but also the following structural formulas (3) to (6).

May be contained in an amount of 30 mol% or less of the total of the structural parts represented by the formula (1). In particular, in the present invention, the content of the structural parts represented by the above formulas (3) to (6) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. When the polyarylene sulfide resin contains the structural parts represented by the above formulas (3) to (6), the bonding manner thereof may be any of a random copolymer and a block copolymer. .

  The polyarylene sulfide resin has the following formula (7) in its molecular structure.

May have a trifunctional structural site represented by or a naphthyl sulfide bond, but is preferably 3 mol% or less, particularly preferably 1 mol%, based on the total number of moles with other structural sites. The following is preferred.

  The physical properties of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.

  The polyarylene sulfide resin used in the present invention preferably has a carboxy group. The ratio of the carboxy group in the polyarylene sulfide resin is not particularly limited as long as the effects of the invention are not impaired, but it is preferable that the polyarylene sulfide resin contains the carboxy group in a ratio of 15 to 200 (μmol / g) in the polyarylene sulfide resin. More preferably, it is contained in the resin at a ratio in the range of 25 to 100 (μmol / g). A ratio of the carboxy group in the polyarylene sulfide resin of 15 (μmol / g) or more is preferable because the affinity with a nonaqueous solvent used for an electrolyte of a nonaqueous electrolyte secondary battery is improved. On the other hand, if it is 200 (μmol / g) or less, the reactivity with the polyolefin becomes excessive, and gelation tends to occur during melt kneading, and gelation with the polyolefin (B1) or the polyolefin resin composition (B). Tend to be suppressed, which is preferable.

(Melt viscosity)
The polyarylene sulfide resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 100 to 2000 (Pa · s), Further, the range of 120 to 1600 (Pa · s) is more preferable because the balance between the fluidity and the mechanical strength is improved.

(Non-Newton index)
The non-Newton index of the polyarylene sulfide resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newton index is preferably in the range of 0.90 to 1.50, and more preferably in the range of 0.95 to 1.20. Such a polyarylene sulfide resin has excellent mechanical properties, fluidity and abrasion resistance. However, the non-Newton index (N value) is obtained by measuring the shear rate and the shear stress under the conditions of 300 ° C., the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40, using a capillograph. , Calculated using the following equation.

[However, SR indicates a shear rate (sec- ¹ ), SS indicates a shear stress (dyne / cm ² ), and K indicates a constant. ] The closer the N value is 1, the closer the PPS is to a linear structure, and the higher the N value, the more the structure is branched.

(Production method)
The method for producing the polyarylene sulfide resin (A) is not particularly limited. For example, 1) a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymer component In addition, a method of polymerizing, 2) a method of adding a dihalogeno aromatic compound in a polar solvent in the presence of a sulfidizing agent or the like and, if necessary, a polyhalogeno aromatic compound or other copolymerization components, and polymerizing the compound; 3) A method in which p-chlorothiophenol is self-condensed by adding other copolymerization components, if necessary, and the like. Among these methods, the method 2) is versatile and preferable. At the time of the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above 2) methods, a hydrous sulfidizing agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno-aromatic compound at such a rate that water can be removed from the reaction mixture, and the dihalogeno-aromatic compound is introduced in the organic polar solvent. And a sulfidizing agent, if necessary, with a polyhalogeno aromatic compound to cause a reaction, and to adjust the amount of water in the reaction system to a range of 0.02 to 0.5 mol per 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by controlling (refer to Japanese Patent Application Laid-Open No. 07-228699), and a method for preparing a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, if necessary. A polyhalogeno aromatic compound or other copolymer component is added, and an alkali metal hydrosulfide and an organic acid alkali metal salt are added to a sulfur source 1 The reaction is carried out while controlling the amount of the organic acid alkali metal salt in the reaction system to 0.01 to 0.9 mol and the amount of water in the reaction system to 0.02 mol or less per 1 mol of the aprotic polar organic solvent. Those obtained by the method (see WO 2010/058713) are particularly preferred. Specific examples of the dihalogeno aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4,4'-dihalodiphenylsulfide, and the above compounds Compounds having an alkyl group having 1 to 18 carbon atoms in the aromatic ring are listed as examples of polyhalogeno aromatic compounds. Zen, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6- And trihalonaphthalene. The halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom.

  The post-treatment method of the reaction mixture containing the polyarylene sulfide resin obtained in the polymerization step is not particularly limited, but, for example, (1) After the completion of the polymerization reaction, first, the reaction mixture may be used as it is or as an acid or base. , And then distill off the solvent under reduced pressure or normal pressure. Then, the solid after distilling off the solvent is washed with water, a reaction solvent (or an organic solvent having an equivalent solubility to a low molecular weight polymer), acetone, methyl ethyl ketone. Washing with a solvent such as alcohol once or twice or more, and further neutralizing, washing with water, filtering and drying, or (2) after the polymerization reaction, adding water, acetone, methyl ethyl ketone, alcohols to the reaction mixture. Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (soluble in the polymerization solvent used, and at least A solvent which is a poor solvent for realylene sulfide) is added as a precipitant to precipitate solid products such as polyarylene sulfide and inorganic salts, and these are separated by filtration, washed and dried, or (3) After the completion of the polymerization reaction, a reaction solvent (or an organic solvent having the same solubility with respect to the low molecular weight polymer) is added to the reaction mixture, and the mixture is stirred, and then filtered to remove the low molecular weight polymer. A method of washing once or twice or more with a solvent such as acetone, methyl ethyl ketone or alcohol, followed by neutralization, washing with water, filtration and drying. (4) After the polymerization reaction is completed, water is added to the reaction mixture to wash with water. A method of adding an acid during filtration and, if necessary, washing with water, treating with an acid, followed by drying. (5) After the completion of the polymerization reaction, the reaction mixture is filtered and, if necessary, once or twice or more with a reaction solvent. Wash Further washing with water, a method of filtering and drying, and the like.

   In the post-treatment methods exemplified in the above (1) to (5), the drying of the polyarylene sulfide resin may be performed in a vacuum, or may be performed in air or in an inert gas atmosphere such as nitrogen. You may.

..Polyolefin having functional group (B1) or polyolefin resin composition containing polyolefin having functional group (B1) (B)
The functional group-containing polyolefin (B1) used in the present invention includes a thermoplastic elastomer having a functional group, a melting point of 300 ° C. or less, and having rubber elasticity at room temperature. Among them, those having an MFR at 310 ° C. in the range of 1 to 100 (g / 10 minutes) are preferable, and those having the MFR in the range of 2 to 50 (g / 10 minutes) are more preferable in terms of heat resistance and ease of mixing. preferable.

  Specific examples of the functional group include at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxy group, a carboxyl group, a mercapto group, an isocyanate group, a vinyl group, an acid anhydride group, and an ester group. Of these, a functional group derived from a carboxylic acid derivative such as an epoxy group or an acid anhydride group, a carboxyl group, or an ester group is more preferred, and an epoxy group is particularly preferred.

  The polyolefin (B1) that can be used in the present invention is preferably obtained by copolymerizing one or more kinds of α-olefins and the vinyl polymerizable compound having the functional group. Examples of the α-olefins include α-olefins having 2 to 8 carbon atoms, such as ethylene, propylene, and butene-1. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylate and alkyl esters thereof, maleic acid, fumaric acid, and itaconic acid. And other unsaturated dicarboxylic acids having 4 to 10 carbon atoms, their mono- and diesters, α, β-unsaturated dicarboxylic acids such as acid anhydrides and derivatives thereof, and glycidyl (meth) acrylate.

  Among these, ethylene having at least one functional group selected from the group consisting of epoxy group, amino group, hydroxy group, carboxyl group, mercapto group, isocyanate group, vinyl group, acid anhydride group and ester group in the molecule. -A propylene copolymer or an ethylene-butene copolymer is preferable, and an ethylene-propylene copolymer or an ethylene-butene copolymer having a carboxyl group is more preferable. These polyolefins can be used alone or in combination of two or more.

  In the present invention, when the polyolefin resin composition (B) containing the polyolefin (B1) having a functional group is used, the ratio of the polyolefin (B1) having a functional group in the polyolefin resin composition (B) is 80 to 100 mass%. % Is preferable. In this case, as a component other than the polyolefin (B1) having a functional group in the polyolefin resin composition (B), a polyolefin (C1) described later is exemplified.

  The ratio between the polyarylene sulfide resin (A) and the polyolefin (B1) or the polyolefin resin composition (B) in the polyarylene sulfide resin particle dispersion of the present invention is not particularly limited as long as the effects of the present invention are not impaired. Preferably, the polyarylene sulfide resin (A) is in the range of 70 to 50 parts by mass, and the polyolefin (B1) or the polyolefin resin composition (B) is in the range of 30 to 50 parts by mass. More preferably, the polyarylene sulfide resin (A) is in the range of 65 to 55 parts by mass, and the polyolefin (B1) or the polyolefin resin composition (B) is in the range of 35 to 45 parts by mass.

  In the polyarylene sulfide resin particle dispersion used in the present invention, depending on the application, in addition to the components described above, as long as the effects of the present invention are not significantly impaired, additives that are generally added to the resin composition may be appropriately used. Can be added. Examples of the additive include recycled resin, silica, talc, kaolin, and calcium carbonate generated from trimming loss of ears and the like, which are added for the purpose of improving and adjusting the formability, productivity, and various physical properties of the laminated porous film. Inorganic particles such as titanium oxide, pigments such as carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, surfactants, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, Additives such as antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents or colorants are included. The ratio of these additives is not particularly limited as long as the effects of the present invention are not impaired. For example, the range of 0.01 to 5 parts by mass is relative to 100 parts by mass of the polyarylene sulfide resin particle dispersion. And more preferably in the range of 0.05 to 5 parts by mass.

-Production of polyarylene sulfide resin particle dispersion The polyarylene sulfide resin particle dispersion of the present invention can be produced, for example, by the following method.
First, the polyarylene sulfide resin (A) and the polyolefin resin composition (B) are melt-kneaded at the above-mentioned ratio at a temperature higher than the melting point of the polyarylene sulfide resin (A), and the extruded kneaded material is obtained. Cooling.

  The temperature at which the melt kneading is performed is not particularly limited as long as it is a temperature equal to or higher than the melting point of the polyarylene sulfide resin, and for example, a range of 270 to 380 ° C.

  As a specific operation method, the polyarylene sulfide resin (A) and the polyolefin resin composition (B) are further mixed, if necessary, with other compounding components using a tumbler or a Henschel mixer. Then, the mixture is put into a melt kneading extruder such as a twin-screw kneading extruder, and the resin component discharge amount ranges from 5 to 500 (kg / hr), the screw rotation speed ranges from 100 to 500 (rpm), and the discharge amount ranges from 4 to It is preferable to perform melt-kneading while appropriately adjusting the range of 40 (kg / hr), and melt under the condition that the ratio (discharge amount / screw rotation speed) is 0.02 to 2 (kg / hr / rpm). It is more preferred to knead.

  In addition, when a reinforcing agent or an additive is added as necessary among the above-mentioned components, it is preferable to introduce the extruder from a side feeder of the twin-screw extruder from the viewpoint of dispersibility. The position of the side feeder is preferably such that the ratio of the distance from the resin input section of the extruder to the side feeder with respect to the entire length of the screw of the twin screw extruder is 0.1 to 0.6. Especially, it is especially preferable that it is 0.2-0.4.

The polyarylene sulfide resin particle dispersion thus melt-kneaded is obtained as strands or pellets, and then may be left at room temperature. However, the kneaded material is quenched as it is by immersing it in water at 5 to 60 ° C. May be cooled. Thereby, the morphology in the melt-kneaded material is effectively maintained.
By producing under such conditions, the polyarylene sulfide resin particle dispersion of the present invention is obtained by dispersing particles comprising the polyarylene sulfide resin (A) in the polyolefin resin composition (B), and The particles have a fraction of particles having a particle size of 100 nm or less in all the particles in a fraction of 10% or more, preferably 15% or more, and more preferably 20% or more. The average particle diameter of the particles is not particularly limited as long as the effects of the present invention are not impaired, but the average particle diameter (D50) is preferably in the range of 100 (nm) to 1 (μm), and more preferably 120 (μm). More preferably, it is in the range of 500 to 500 (nm).

  The polyarylene sulfide resin particle dispersion obtained in this manner is mixed with a thermoplastic resin such as an olefin resin as a filler, so to speak, to give a molded article of the thermoplastic resin with the thermoplastic resin. While maintaining various properties such as mechanical strength of the resin, it is possible to impart excellent heat resistance, particularly heat shrinkage resistance.

-Thermoplastic resin composition The thermoplastic resin composition of the present invention is characterized in that particles composed of a polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300C in the range of 100 to 2000 (Pas) are functional. Dispersed in a polyolefin resin composition (B) containing a polyolefin having a group (B1) or a polyolefin having a functional group (B1) and a thermoplastic resin (C) having a lower melting point than the polyarylene sulfide resin. A thermoplastic resin composition comprising:
The particles are characterized in that the proportion of particles having a particle size of 100 nm or less in all the particles is 10% or more in fractions.

  The proportion of each component of the thermoplastic resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but the particles comprising the polyarylene sulfide resin (A) and the polyolefin (B1) or It is preferable that the thermoplastic resin (C) is in the range of 30 to 90 parts by mass with respect to the total mass of 10 to 70 parts by mass with the polyolefin resin composition (B), and the polyarylene sulfide resin (A ), And the ratio of the polyolefin (B1) or the polyolefin resin composition (B) is in the range of 70 to 50 parts by mass of the polyarylene sulfide resin (A). ) It is more preferably in the range of 30 to 50 parts by mass.

  Such a thermoplastic resin composition, 10 to 70 parts by weight of the polyarylene sulfide resin particle dispersion and 30 to 90 parts by weight of the thermoplastic resin (C), lower than the melting point of the polyarylene sulfide resin, And it can be manufactured by melt-kneading at a temperature higher than the melting point of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C).

  Here, the thermoplastic resin (C) used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but it is 265 which is a melting point generally possessed by the polyarylene sulfide resin as a particle component. Any thermoplastic resin having a melting point lower than the range of ° C. to 350 ° C. may be used, and examples thereof include thermoplastic resins such as polyamide, polyester, polycarbonate, polystyrene, ABS, and polyolefin, and a thermoplastic resin selected from such a group. The polymer alloy can be used alone or in combination of two or more thermoplastic resins.

  Of these, from the viewpoint of having sufficient heat resistance to the increase in the amount of heat generated due to the increase in electric output in recent years, preferably, the melting point is 170 ° C. or more, and the melting point is in the range of less than the melting point of the polyarylene sulfide resin. A thermoplastic resin, or an elastomer or rubber having a softening point of preferably 50 ° C. or more, more preferably 70 to 200 ° C., is mentioned as a preferred resin group, and specifically, polyamide 6 (6-nylon), polyamide 66 ( Polyamides having an aliphatic skeleton such as 6,6-nylon) or polyamide 12 (12-nylon) and polyamides having an aromatic skeleton such as polyamide 6T (6T-nylon) and polyamide 9T (9T-nylon) have melting points. Polyamide, polybutylene terephthalate, polyisobutylene having a temperature of 170 ° C. or more, preferably 170 to 310 ° C. Butyl terephthalate, polyethylene terephthalate or polycyclohexene terephthalate has a melting point of 220 ° C. or more, preferably a polyester resin having a range of 220 to 280 ° C., and polystyrene, and further has a melting point of 220 ° C. or more, preferably 220 to 280 ° C. Certain syndiotactic polystyrenes are mentioned as preferred thermoplastics.

  Among these, the polyarylene sulfide resin particle dispersion of the present invention is excellent in the effect of improving the heat shrinkage resistance while maintaining various properties of the polyolefin, for example, mechanical strength (elastic modulus), and further excellent in compatibility. Therefore, it is preferable to use the polyolefin together with the polyolefin (C1).

  The type of the polyolefin (C1) used in the present invention is not limited, and for example, a homopolymer, a copolymer or a polymer obtained by polymerizing a monomer such as ethylene, propylene, butene, methylpentene, hexene or octene as a raw material is used. Examples include a multi-stage polymer, and two or more different homopolymers, copolymers, or multi-stage polymers can be used in combination.

For example, when polyethylene is used as the polyolefin (C1), the weight average molecular weight is preferably in the range of 5 × 10 ⁵ or more and 15 × 10 ⁶ or less. Types of polyethylene include ultra high molecular weight polyethylene, high density polyethylene, medium density polyethylene and low density polyethylene. The weight average molecular weight of the ultrahigh molecular weight polyethylene is preferably from 1 × 10 ⁶ to 15 × 10 ⁶ , more preferably from 1 × 10 ^{6 to} 5 × 10 ⁶ . By setting the weight average molecular weight in a range of 15 × 10 ⁶ or less, melt extrusion can be facilitated. In addition, a polyethylene having a weight average molecular weight of 5 × 10 ⁵ or more, a polyethylene having a weight average molecular weight of 1 × 10 ⁴ or more and less than 5 × 10 ⁵ , and a weight average molecular weight of 1 × 10 ⁴ to 4 × 10 ⁶ are used. Of polypropylene, polybutene-1 having a weight average molecular weight of 1 × 10 ⁴ to 4 × 10 ⁶ , polyethylene wax having a weight average molecular weight of 1 × 10 ³ or more to less than 1 × 10 ⁴ , and a weight average molecular weight of 1 × 10 ⁴ It is also preferable to mix at least one selected from the group consisting of ethylene / α-olefin copolymers in a range of from 4 × 10 ⁶ to 4 × 10 ⁶ .

When polypropylene is used as the polyolefin, the weight average molecular weight is not particularly limited, but is preferably in the range of 1 × 10 ⁴ to 4 × 10 ⁶ .

When an ethylene / α-olefin copolymer is used together with a polyolefin, particularly polyethylene having a weight-average molecular weight of 5 × 10 ⁵ or more, the α-olefin may be propylene, butene-1, hexene-1, pentene-1, 4- Methylpentene-1, octene, vinyl acetate, methyl methacrylate, styrene and the like are preferred.

  Among these, as the polyolefin (C1) used in the present invention, high-density polyethylene, ultrahigh-molecular-weight polyethylene, or polypropylene is preferable, and a microporous sheet or film is produced using the pore-forming agent (D) described below. In this case, high-density polyethylene or ultra-high-molecular-weight polyethylene is preferable, and when a microporous sheet or film is produced using the β crystal nucleating agent (E), polypropylene is more preferable.

  The ratio of the polyarylene sulfide resin particle dispersion to the thermoplastic resin (C) in the thermoplastic resin composition used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. It is preferable that the particle dispersion is in the range of 10 to 70 parts by mass and the thermoplastic resin (C) is in the range of 30 to 90 parts by mass, and the polyarylene sulfide resin particle dispersion is in the range of 20 to 50 parts by mass. More preferably, the content of the thermoplastic resin (C) is in the range of 50 to 80 parts by mass. Within this range, various properties of the thermoplastic resin (C), for example, mechanical strength, can be maintained, and excellent heat resistance, particularly heat shrinkage resistance can be exhibited, which is preferable.

  To the thermoplastic resin composition used in the present invention, depending on the application, in addition to the components described above, within the range not significantly impairing the effects of the present invention, additives generally mixed with the resin composition can be appropriately added. . Examples of the additive include recycled resin, silica, talc, kaolin, and calcium carbonate generated from trimming loss of ears and the like, which are added for the purpose of improving and adjusting the formability, productivity, and various physical properties of the laminated porous film. Inorganic particles such as titanium oxide, pigments such as carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, surfactants, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, Additives such as antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents or colorants are included. The ratio of these additives is not particularly limited as long as the effects of the present invention are not impaired. For example, the ratio is 0.01 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition. And more preferably in the range of 0.05 to 5 parts by mass.

-Method for producing thermoplastic resin composition The thermoplastic resin composition of the present invention comprises 10 to 70 parts by mass of the polyarylene sulfide resin particle dispersion and 30 to 90 parts by mass of the thermoplastic resin (C). Melt kneading at a temperature lower than the melting point of the arylene sulfide resin and higher than the melting point of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). (Hereinafter, sometimes referred to as step (1)).

  Step (1) is a step in which the polyarylene sulfide resin particle dispersion of the present invention is blended with the thermoplastic resin (C) and, if necessary, other additives and melt-kneaded. Specifically, first, a predetermined amount of a polyarylene sulfide resin particle dispersion, a thermoplastic resin (C), and an additive, if necessary, are added in various forms such as powder, beret, and strip, as required. After the pre-mixing, the mixture is put into a melt kneader, and in a temperature range higher than the melting point of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C), and a polyarylene. The resin is heated to a temperature lower than the melting point of the sulfide resin (A), melt-kneaded to obtain a thermoplastic resin composition, and the extruded kneaded material is cooled.

  The raw material is a mixture of the polyarylene sulfide resin particle dispersion and the thermoplastic resin (C) in the range of 10 to 70 parts by mass of the polyarylene sulfide resin particle dispersion, and 30 to 90 parts by mass of the thermoplastic resin (C). It is preferable to mix in the range of 20 to 50 parts by mass of the polyarylene sulfide resin particle dispersion and more preferably in the range of 50 to 80 parts by mass of the thermoplastic resin (C).

  At that time, the temperature at which the melt-kneading is performed is not particularly limited as long as the effects of the present invention are not impaired, but is lower than the melting point of the polyarylene sulfide resin, and the polyolefin (B1) or the polyolefin resin composition (B) and The range of the temperature higher than any melting point of the thermoplastic resin (C) is mentioned.

  As a specific operation method, the polyarylene sulfide resin (A) and the polyolefin resin composition (B) are further mixed, if necessary, with other compounding components uniformly using a tumbler or a Henschel mixer, and the like. It is charged into a melt-kneading extruder such as a twin-screw kneading extruder, and the resin component is discharged in a range of 5 to 500 (kg / hr), a screw rotation speed is in a range of 100 to 500 (rpm), and a discharge amount is 4 to 40. (Kg / hr), it is preferable to perform melt-kneading while appropriately adjusting the range, and the melt-kneading is performed under the condition that the ratio (discharge amount / screw rotation speed) is 0.02 to 2 (kg / hr / rpm). More preferably,

  In addition, when a reinforcing agent or an additive is added as necessary among the above-mentioned components, it is preferable to introduce the extruder from a side feeder of the twin-screw extruder from the viewpoint of dispersibility. The position of the side feeder is preferably such that the ratio of the distance from the resin input section of the extruder to the side feeder with respect to the entire length of the screw of the twin screw extruder is 0.1 to 0.6. Especially, it is especially preferable that it is 0.2-0.4.

  The thermoplastic resin composition thus melt-kneaded is allowed to stand at room temperature after being extruded into strands, or is cooled by rapid cooling or the like by immersing the kneaded material in water at 5 to 60 ° C., and cut. Into granules such as pellets and chips.

  When manufactured under such conditions, the thermoplastic resin composition of the present invention is characterized in that the particles comprising the polyarylene sulfide resin (A) are formed of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin. A resin is obtained which is dispersed in a resin composition containing the resin (C), and in which the ratio of the particles having a particle size of 100 nm or less to all the particles is 10% or more in fractions. The average particle diameter of the particles may be in the range described above.

-Manufacturing method of molded article The molded article of the present invention is obtained by converting the thermoplastic resin composition to a temperature lower than the melting point of the polyarylene sulfide resin (A) and the polyolefin (B1) or the polyolefin resin composition (B). And molding a thermoplastic resin composition heated to a temperature range higher than any melting point of the thermoplastic resin (C), and the particles made of the polyarylene sulfide resin (A) become the polyolefin (B1) or The ratio of particles having a particle diameter of 100 nm or less in all the particles dispersed in a resin composition containing the polyolefin resin composition (B) and the thermoplastic resin (C) is a fraction. To obtain a molded product of 10% or more.

  The molding method is not particularly limited as long as the effects of the present invention are not impaired, and known and commonly used methods can be used. For example, injection molding, compression molding, extrusion molding of composites and pipes, pultrusion molding, blow molding, transfer Various molding methods such as molding can be given, in particular, spinning after melt-kneading and stretching to form fibers, or melt-kneading as described later to form a sheet or film, and stretching to form a sheet or film Is preferred.

  By manufacturing under such conditions, the molded article of the present invention is characterized in that the particles comprising the polyarylene sulfide resin (A) have a lower melting point than the thermoplastic elastomer (B) having a functional group and the polyarylene sulfide resin. It is obtained that the particles are dispersed in a matrix containing the plastic resin (C), and the ratio of the particles having a particle diameter of 100 nm or less to all the particles is 10% or more in fractions. The average particle size of the particles may be in the above range. The average particle diameter of the particles may be in the range described above.

-Method for producing sheet or film The sheet or film of the present invention uses the thermoplastic resin composition obtained in the step (1) and has a lower melting point than the polyarylene sulfide resin and the polyolefin (B1). Alternatively, the polyolefin resin composition (A) is formed by heating the polyolefin resin composition (B) and the thermoplastic resin (C) to a temperature range higher than the melting point of any of the polyolefin resin composition (B) and the thermoplastic resin composition to form a sheet. Particles are dispersed in a resin composition containing the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C), and the particles have a particle diameter of 100 nm in all the particles. It is possible to obtain a sheet or film in which the ratio of the following particles is 10% or more in fractions (hereinafter referred to as step (2)). There is).

That is, 10 to 70 parts by mass of the polyarylene sulfide resin particle dispersion of the present invention and 30 to 90 parts by mass of the thermoplastic resin (C) are lower than the melting point of the polyarylene sulfide resin and the polyolefin (B1 ) Or melt-kneading in a temperature range higher than the melting point of any of the polyolefin resin composition (B) and the thermoplastic resin (C) to obtain a thermoplastic resin composition (1);
Thermoplastic resin heated to a temperature lower than the melting point of the polyarylene sulfide resin and higher than the melting point of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). A resin composition comprising a sheet or film of the composition, wherein the particles of the polyarylene sulfide resin (A) contain the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). A step (2) of obtaining a sheet or film in which the ratio of particles having a particle size of 100 nm or less to all the particles is 10% or more by a fraction.

  The thermoplastic resin composition obtained in the step (1) is once cooled, pelletized, and then extruded again through an extruder, or directly or through another extruder, from a die, cast roll or With a roll such as a roll take-up machine, it is preferable that the die (lip width) / sheet or film thickness be in the range of 1.1 to 40, and more preferably in the range of 2 to 20. Is more preferred. As the die, it is usually preferable to use a die for a sheet or film having a rectangular die shape, but a double cylindrical hollow die, an inflation die and the like can also be used. In the case of a die for sheet or film, the gap (lip width) of the lip portion of the die is usually preferably 0.1 to 5 mm, and when extruded, the gap is set to the polyolefin (B1) or the polyolefin resin composition (B). A temperature higher than any melting point of the thermoplastic resin (C) and a range not higher than the melting point of the polyarylene sulfide resin (A), preferably the polyolefin (B1) or the polyolefin resin composition (B) and the The higher of the melting point of the thermoplastic resin (C) + 10 ° C. or more, more preferably the higher of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). Melting point +10 to melting point + 50 ° C, more preferably the polyolefin (B1) or Serial to heat the polyolefin resin composition (B) and the temperature of any higher melting point range of + 20 to 30 ° C. of the thermoplastic resin (C). The extrusion rate of the heated solution is preferably in the range of 0.2 to 50 (m / min).

  The sheet or film of the thermoplastic resin composition thus extruded from the die is cooled to form a sheet or film. Cooling is preferably performed at a rate of 50 ° C./min or more at least up to the crystallization temperature or lower. If the cooling rate is less than 50 ° C./min, the degree of crystallinity increases, and it tends to be difficult to obtain a sheet or film suitable for stretching.

  In this manner, the polyolefin (B1) or the resin composition containing the polyolefin resin composition (B) and the thermoplastic resin (C) is used as a matrix, and at least particles of the polyarylene sulfide resin (A) are contained in the matrix. Can be immobilized. When other additive components such as an antioxidant compounded as necessary are added, the particles of the polyarylene sulfide resin (A) are mixed with other additive components such as an antioxidant compounded as necessary. The agent component can fix a phase separation structure dispersed in the continuous phase of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). As a cooling method, a method of directly contacting with cold air, cooling water, or another cooling medium, a method of contacting with a roll cooled by a refrigerant, or the like can be used. The draft ratio ((roll take-up speed) / (flow rate of resin flowing out of the die lip calculated from the density)) when taken up by a roll is preferably from 1 to 300 times, more preferably from the viewpoint of air permeability and moldability. It is 1 to 200 times, more preferably 1 to 100 times.

  In the present invention, the thickness of the sheet or film varies depending on its use, and can be any thickness, but is usually 5 μm to 5 mm, preferably 5 to 500 μm, more preferably 10 to 150 μm, and further preferably It is 20 to 100 μm, particularly preferably 30 to 70 μm.

  The sheet or film of the present invention thus obtained has excellent heat resistance, especially heat shrink resistance. When the thermoplastic resin (C1) is a polyolefin (C1), the surface releasability of various surface protective films and transfer foils can be improved using the sheet or film having excellent heat shrink resistance of the present invention. It can be suitably used as a laminate obtained by laminating a polyolefin by extrusion lamination on a base film such as a film or a polyester film.

  When the thermoplastic resin composition contains the pore forming agent (D) or the β crystal nucleating agent (E), the sheet or film material obtained in the step (2) is converted into a porous material described later. Through the step (3) of forming into a layer, a microporous sheet or film can be obtained.

-Microporous sheet or film The microporous sheet or film of the present invention is obtained by forming a porous sheet or film obtained by melt-molding the thermoplastic resin composition of the present invention,
Particles comprising the polyarylene sulfide resin (A) are dispersed in a resin composition containing the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C), and The particle is characterized in that the proportion of particles having a particle size of 100 nm or less in all the particles is 10% or more in fractions.

  In the method for producing a microporous sheet or film of the present invention, in the step (1), in addition to the polyarylene sulfide resin particle dispersion and the thermoplastic resin (C), a pore-forming agent (D) or β-crystal There is a step (3) of kneading the nucleating agent (E), making the sheet or film obtained in the step (2) porous, in addition to the steps (1) and (2).

That is, 10 to 70 parts by mass of the polyarylene sulfide resin particle dispersion of the present invention, 30 to 90 parts by mass of the thermoplastic resin (C), and the pore forming agent (D) or the β crystal nucleating agent (E). Melt kneading in a temperature range lower than the melting point of the polyarylene sulfide resin and higher than the melting point of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). To obtain a thermoplastic resin composition (α) (1),
A thermoplastic resin composition (α) heated to a temperature lower than the melting point of the polyarylene sulfide resin and higher than the melting points of the polyolefin resin composition (B) and the thermoplastic resin (C). The particles comprising the polyarylene sulfide resin (A) and the pore-forming agent (D) or the β crystal nucleating agent (E) are formed into a sheet or a film, and the polyolefin (B1) or the polyolefin resin composition (B) A sheet or a film which is dispersed in a resin composition containing the thermoplastic resin (C), and in which the ratio of particles having a particle size of 100 nm or less to all particles is 10% or more in fractions. Step (2) of obtaining a material (β),
The method further includes a step (3) of making the sheet or film material (β) obtained in the step (2) porous.

  Through the steps (1), (2) and (3), the resin composition containing the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C) is used as a matrix, Particles comprising a polyarylene sulfide resin (A) are contained in the matrix as a dispersed phase, and the ratio of the particles having a particle size of 100 nm or less to all the particles is 10% or more in a fraction. , A microporous sheet or film (a so-called microporous membrane) is obtained. The average particle diameter of the particles may be in the range described above.

  The step (3) of forming a porous body is roughly classified into a case where a pore forming agent (D) is used and a case where a β crystal nucleating agent (E) is used. First, the case where the pore forming agent (D) is used will be described.

  As the pore-forming agent (D), known and commonly used ones can be used, but it is not particularly limited as long as it can be dissolved in a solvent used in a step of making the sheet or film porous as described below. For example, calcium carbonate fine particles are preferable, but inorganic fine particles such as magnesium sulfate fine particles, calcium oxide fine particles, calcium hydroxide fine particles, silica fine particles, and a solid or liquid solvent at room temperature can also be used.

  Solvents that are liquid at room temperature include nonane, decane, decalin, paraxylene, undecane, dodecane, aliphatic or cyclic hydrocarbons such as liquid paraffin, and mineral oil fractions whose boiling points correspond to these, as well as dibutyl phthalate, dioctyl A phthalic acid ester which is liquid at room temperature such as phthalate may be mentioned, and it is preferable to use a non-volatile liquid solvent such as liquid paraffin.

  Further, as a solvent which is solid at room temperature, the solvent becomes a miscible state with the polyolefin in a heat-melt kneading state, but a solvent in a solid state at room temperature can be used, and stearyl alcohol, ceryl alcohol, paraffin wax and the like can be used. If only a solid solvent is used, uneven stretching or the like may occur, so it is preferable to use a liquid solvent in combination.

  The ratio of the pore-forming agent (D) in the thermoplastic resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired. However, in consideration of the strength and toughness of a sheet or a porous film, The content is preferably in the range of 25 to 250 parts by mass with respect to the total of 100 parts by mass of the particles made of the polyarylene sulfide resin (A), the polyolefin resin composition (B) and the thermoplastic resin (C), More preferably, it is in the range of 10 to 120 parts by mass.

  In the case of using the pore-forming agent (D), the step (3) is to form a microporosity by eluting the pore-forming agent (D) using an acidic aqueous solution or a polar solvent. A film production step, specifically, a step (3a) of removing the pore-forming agent (D) after stretching the sheet or film material (β), and removing the pores from the sheet or film material (β). A step (3b) of stretching after removing the forming agent (D), or a step (3c) of removing the pore forming agent (D) after stretching the sheet or film material (β), and further stretching. .

  In any of the processes (3a) to (3c), the stretching is performed by heating the sheet or film material (β) and then performing the stretching by a usual tenter method, a roll method, an inflation method, a rolling method or a combination of these methods. Perform at a magnification of. The stretching may be uniaxial stretching or biaxial stretching, but biaxial stretching is preferred. In the case of biaxial stretching, any of simultaneous biaxial stretching, sequential stretching or multi-stage stretching (combination of simultaneous biaxial stretching and sequential stretching) may be used, but sequential biaxial stretching is particularly preferred. Stretching increases the mechanical strength.

  The stretching ratio varies depending on the thickness of the sheet or film material (β), but is preferably at least 2 times, more preferably 3 to 30 times when performing uniaxial stretching. In biaxial stretching, at least 2 times or more in any direction, preferably 4 times or more in area ratio, more preferably 6 times or more in area ratio. By setting the area magnification to 4 times or more, the piercing strength can be improved. On the other hand, when the area magnification is more than 100 times, there is a tendency that restrictions are imposed on a stretching apparatus, a stretching operation and the like.

  The stretching temperature is preferably set to be equal to or lower than the melting point of the polyolefin (C1) + 10 ° C., and more preferably in the range from the glass transition point to lower than the melting point. When the stretching temperature is equal to or lower than the melting point + 10 ° C., the melting of the polyolefin (C1) is suppressed, and the molecular chains can be oriented by stretching. When the stretching temperature is equal to or higher than the glass transition point, the polyolefin (C1) is sufficiently softened, and the film is prevented from being broken in the stretching. However, when performing sequential stretching or multi-stage stretching, the primary stretching may be performed below the glass transition point. Here, the glass transition point and the melting point refer to values determined by measuring the temperature characteristics of dynamic viscoelasticity based on ASTM D 4065. As measurement conditions, the measurement temperature range is −20 to 200 ° C., the sine wave frequency is 100 Hz, and the heating rate is 2 ° C./min.

  Depending on the desired physical properties, stretching can be performed with a temperature distribution in the film thickness direction, or sequential stretching or multi-stage stretching in which primary stretching is performed at a relatively low temperature and then secondary stretching is performed at a higher temperature. By stretching while providing a temperature distribution in the film thickness direction, a microporous film generally having excellent mechanical strength can be obtained. As the method, for example, a method disclosed in JP-A-7-188440 can be applied.

  For removing the pore-forming agent (D), a solvent capable of dissolving the pore-forming agent (D) (hereinafter, referred to as a removal solvent) is used. By removing the pore forming agent (D) uniformly finely dispersed using the removing solvent, a microporous sheet or film can be obtained. Specific examples of the removal solvent include, for example, acidic aqueous solutions such as hydrochloric acid, methylene chloride, chlorinated hydrocarbons such as carbon tetrachloride, pentane, hexane, hydrocarbons such as heptane, fluorinated hydrocarbons such as ethane trifluoride, Examples include ethers such as diethyl ether and dioxane, and volatile solvents such as methyl ethyl ketone. As the removing solvent, in addition to the above, a solvent having a surface tension at 25 ° C. of 24 mN / m or less, which is disclosed in JP-A-2002-256099, can be used. Fluorine compounds such as ether, cyclic hydrofluorocarbon, perfluorocarbon, perfluoroether, normal paraffin having 5 to 10 carbon atoms, isoparaffin having 6 to 10 carbon atoms, aliphatic ether having 6 or less carbon atoms, cyclopentane, etc. Cycloparaffin, aliphatic ketones such as 2-pentanone, methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, isobutanol, aliphatic alcohols such as 2-pentanol, propyl acetate, tert-butyl acetate, Seca acetate Daribuchiru, ethyl acetate, isopropyl acetate, isobutyl acetate, methyl formate, ethyl formate, may be mentioned isopropyl formate, isobutyl formate, an aliphatic ester and ethyl propionate. By using a solvent having such a surface tension, the shrinkage and densification of the network caused by the surface tension of the gas-liquid interface generated inside the microporous at the time of drying after removing the pore-forming agent (d) is suppressed. As a result, the porosity and permeability of the microporous membrane are further improved.

  The method of removing the pore-forming agent (D) is a method of dipping the stretched sheet or film material (β) in a removal solvent, a method of showering the stretched sheet or film material (β) with the removal solvent, or a method of removing these. It can be performed by a method based on a combination or the like. The removal solvent is preferably used in an amount of 300 to 30,000 parts by mass based on 100 parts by mass of the sheet or film material (β). The removal treatment with the removal solvent is preferably performed until the amount of the remaining pore-forming agent becomes less than 1% by mass based on the amount of the pore-forming agent added.

  On the other hand, when the β crystal nucleating agent (E) is used, the step (3) is called a so-called dry method in which a sheet or a film mainly containing polypropylene having β crystals is stretched to form microporous material. This is a step of producing a microporous membrane, for example, a step (3d) of stretching the sheet or film material (β).

  Examples of the β crystal nucleating agent (E) used in the present invention include the following. However, the β crystal nucleating agent is not particularly limited as long as it increases the production and growth of β crystal of polypropylene. May be used in combination.

  Examples of the β crystal nucleating agent (E) include an amide compound; a tetraoxaspiro compound; a quinacridone; an iron oxide having a nanoscale size; potassium 1,2-hydroxystearate, magnesium benzoate or magnesium succinate, and phthalate. Alkali or alkaline earth metal salts of carboxylic acids such as magnesium silicate; aromatic sulfonic acid compounds such as sodium benzenesulfonate and sodium naphthalenesulfonate; di- or triesters of di- or tribasic carboxylic acids A phthalocyanine pigment represented by phthalocyanine blue, etc .; a binary compound comprising an organic dibasic acid and an oxide, hydroxide or salt of a Group IIA metal of the periodic table; a composition comprising a cyclic phosphorus compound and a magnesium compound Things That. As a commercially available product of such a β crystal nucleating agent, a β crystal nucleating agent “NJESTA NU-100” manufactured by Nippon Rika Co., Ltd., and as a specific example of the polypropylene resin to which the β crystal nucleating agent is added, a polypropylene manufactured by Aristech "Bepol B-022SP", polypropylene "Beta (β) -PP BE60-7032" manufactured by Borealis, polypropylene "BNX BETAPP-LN" manufactured by Mayzo, and the like.

  The ratio of the β crystal nucleating agent (E) in the thermoplastic resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired. However, considering the strength and toughness of a sheet or a porous film. The total amount is preferably from 0.0001 to 10 parts by mass, more preferably from 0.1 to 10 parts by mass, based on 100 parts by mass of the total of the polyolefin (B1) or the polyolefin resin composition (B) and the thermoplastic resin (C). The range of 001 to 5 parts by mass is more preferable, and the range of 0.01 to 1 part by mass is most preferable. When the content is 0.0001 parts by mass or more, β crystals can be generated and grown, sufficient β activity can be secured even when used as a separator, and desired air permeability can be obtained. Parts or less is preferable because bleeding of the β crystal nucleating agent can be suppressed.

  In the step (3d), the stretching is performed at a predetermined magnification by heating the sheet or film material (β) and then using a usual tenter method, a roll method, an inflation method, a rolling method or a combination of these methods. The stretching may be uniaxial stretching or biaxial stretching, but biaxial stretching is preferred. In the case of biaxial stretching, any of simultaneous biaxial stretching, sequential stretching or multi-stage stretching (combination of simultaneous biaxial stretching and sequential stretching) may be used, but sequential biaxial stretching is particularly preferred. Stretching increases the mechanical strength.

  The stretching ratio varies depending on the thickness of the sheet or film material (β), but is preferably at least 2 times, more preferably 3 to 30 times when performing uniaxial stretching. In biaxial stretching, at least 2 times or more in any direction, preferably 4 times or more in area ratio, more preferably 6 times or more in area ratio. By setting the area magnification to 4 times or more, the piercing strength can be improved. On the other hand, when the area magnification is more than 100 times, there is a tendency that restrictions are imposed on a stretching apparatus, a stretching operation and the like.

  In the case of using the β crystal nucleating agent (E), in the stretching step, the film may be stretched uniaxially or longitudinally or biaxially. When performing biaxial stretching, simultaneous biaxial stretching may be performed, or sequential biaxial stretching may be performed. When producing the microporous heat-resistant sheet of the present invention, sequential biaxial stretching is more preferable because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled.

  When sequential biaxial stretching is used, the stretching temperature needs to be changed as appropriate depending on the composition, melting point, crystallinity, etc. of the thermoplastic resin composition (α) to be used, but the stretching temperature in longitudinal stretching is generally from 0 to 130 ° C. Preferably, it is controlled in the range of 10 to 120 ° C, more preferably 20 to 110 ° C. Further, the longitudinal stretching ratio is preferably 2 to 10 times, more preferably 3 to 8 times, and still more preferably 4 to 7 times. By performing longitudinal stretching within the above range, an appropriate hole origin can be developed while suppressing breakage during stretching.

  On the other hand, the stretching temperature in the transverse stretching is generally 100 to 160 ° C, preferably 110 to 150 ° C, and more preferably 120 to 140 ° C. Further, the preferred transverse stretching ratio is 2 to 10 times, more preferably 3 to 8 times, and still more preferably 4 to 7 times. By performing the horizontal stretching within the above range, the origin of the holes formed by the vertical stretching can be appropriately enlarged, and a fine porous structure can be developed.

  The stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10000% / min, and further preferably 2500 to 8000% / min.

  The sheet or film material (β) obtained through the step (2), and the microporous sheet or film obtained through the step (3) are then subjected to the following steps as long as the polyolefin (C1) does not melt. Known post-treatment steps such as a drying treatment, a heat treatment, a cross-linking treatment, and a hydrophilic treatment can be performed.

  Examples of the drying treatment include a method of drying by a heat drying method or an air drying method. The drying temperature is preferably a temperature not higher than the crystal dispersion temperature of the polyolefin (C1), and particularly preferably a temperature lower than the crystal dispersion temperature by 5 ° C. or more.

  By the drying treatment, the content of the removal solvent remaining in the microporous sheet or film is preferably adjusted to 5% by mass or less (the film mass after drying is set to 100% by mass), and 3% by mass or less. Is more preferable. If the drying solvent is insufficient and a large amount of the removal solvent remains in the film, the porosity decreases in the subsequent heat treatment, and the permeability deteriorates.

  In the present invention, it is preferable to perform a heat treatment at a temperature in the range of 100 to 170 ° C. as a post-treatment. The heat treatment stabilizes the crystal, makes the lamella layer uniform, and improves dimensional stability. As the heat treatment method, any of a heat stretching treatment, a heat setting treatment and a heat shrink treatment may be used, and these are appropriately selected according to the physical properties required for the sheet or film. These heat treatments are preferably performed at a temperature higher than or equal to the crystallization temperature of the polyolefin (C1) in the sheet or film and lower than or equal to the melting point, and more preferably at an intermediate temperature between the crystallization temperature and the melting point.

  The hot stretching treatment is performed by a commonly used tenter method, a roll method or a rolling method, and is preferably performed in at least one direction at a stretch ratio of 1.01 to 2.0 times, preferably 1.01 to 1.5 times. More preferably, it is performed within the range.

  The heat setting is performed by a tenter method, a roll method, or a rolling method. The heat shrinkage treatment may be performed by a tenter method, a roll method or a rolling method, or may be performed by using a belt conveyor or floating. Note that the heat shrinking treatment is preferably performed in at least one direction in a range of 50% or less, and more preferably in a range of 30% or less.

  It should be noted that the above-described heat stretching, heat setting, and heat shrinking may be performed in combination. In particular, when the heat stretching treatment is performed after the heat setting treatment, the permeability of the obtained sheet or film is improved and the pore diameter is increased. Further, it is preferable to perform a heat shrinkage treatment after the heat stretching treatment since a sheet or film having a low shrinkage ratio and high strength can be obtained.

  Further, as the crosslinking treatment, α-rays, β-rays, γ-rays, electron beams, etc. are used as ionizing radiation, and ionizing radiation is performed at an electron dose of 0.1 to 100 Mrad at an accelerating voltage of 100 to 300 kV to form a microporous membrane. Can be crosslinked. Thereby, the meltdown temperature can be improved.

  In addition, as the hydrophilization treatment, a monomer graft, a surfactant treatment, a corona discharge treatment, or the like is performed to hydrophilize a microporous sheet or film. The monomer grafting treatment is preferably performed after ionizing radiation.

  When performing a surfactant treatment using a surfactant as a hydrophilic treatment, any of a nonionic surfactant, a cationic surfactant, an anionic surfactant or a zwitterionic surfactant can be used. However, it is preferable to use a nonionic surfactant. When a surfactant is used, the surfactant is converted to an aqueous solution or a solution of a lower alcohol such as methanol, ethanol, or isopropyl alcohol, and dipped or hydrophilized by a method using a doctor blade. The sheet or film subjected to the hydrophilic treatment is then dried. At this time, in order to improve the permeability, it is preferable to perform a heat treatment at a temperature lower than the melting point of the microporous sheet or film while preventing shrinkage. As a method of performing a heat treatment while preventing shrinkage, for example, a method of performing a heat treatment while stretching is used.

  Further, as a post-treatment step, a known surface treatment such as a corona treatment machine, a plasma treatment machine, an ozone treatment machine, or a flame treatment machine can be performed.

-Non-aqueous electrolyte secondary battery and separator The microporous sheet or film of the present invention thus obtained is a non-aqueous solvent (organic polarity) contained in a non-aqueous electrolyte used for a non-aqueous electrolyte secondary battery. Solvent), it can be used as a separator for the non-aqueous electrolyte secondary battery. Further, since it has heat resistance, particularly heat shrinkage, it can be used as a single-layer separator. Can also.
Hereinafter, the non-aqueous electrolyte secondary battery used in the present invention will be described.

  A non-aqueous electrolyte secondary battery used in the present invention includes the non-aqueous electrolytic solution of the present invention, a positive electrode, and a negative electrode. Specifically, it has a positive electrode plate in which a positive electrode active material layer is provided on one surface side of a positive electrode current collector, and a negative electrode plate in which a negative electrode active material layer is provided on one surface side of a negative electrode current collector. Can be exemplified. The positive electrode plate and the negative electrode plate are opposed to each other with a non-aqueous electrolyte of the present invention and a separator provided in the non-aqueous electrolyte interposed therebetween. Specific examples of the nonaqueous electrolyte secondary battery used in the present invention include, for example, a lithium ion secondary battery.

  As the positive electrode current collector and the negative electrode current collector, for example, a metal foil made of a metal such as aluminum, copper, nickel, and stainless steel can be used.

As the positive electrode active material used for the positive electrode active material layer, a lithium-containing composite oxide is preferably used. For example, LiMnO ₂ , LiFeO ₂ , LiCoO ₂ , LiMn ₂ O ₄ , Li ₂ FeSiO ₄ , LiNi _1/3 Co _{1 And} lithium-containing composite oxides such as _{/ 3} Mn _1/3 O ₂ and LiFePO ₄ .

  Examples of the negative electrode active material used for the negative electrode active material layer include materials capable of inserting and extracting lithium. Examples of such a material include carbon materials such as graphite and amorphous carbon, and oxide materials such as indium oxide, silicon oxide, tin oxide, zinc oxide, and lithium oxide.

  Alternatively, as the negative electrode active material, lithium metal or a metal material which can form an alloy with lithium can be used. Examples of the metal that can form an alloy with lithium include Cu, Sn, Si, Co, Mn, Fe, Sb, and Ag, and are made of binary or ternary containing these metals and lithium. Alloys can also be used. These negative electrode active materials may be used alone or in combination of two or more.

  Further, the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte. As the non-aqueous solvent, for example, an aprotic solvent can be preferably exemplified. Examples of the aprotic solvent include a cyclic aprotic solvent and a chain aprotic solvent. Examples of the cyclic aprotic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, and 2,3-pentylene carbonate. And cyclic esters such as γ-butyrolactone and γ-valerolactone.

  Examples of the linear aprotic solvent include, for example, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethyl propyl carbonate, methyl trifluoroethyl carbonate And chain carbonates such as ethyl butyl carbonate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate.

  As the non-aqueous solvent, a carbonate-based solvent is preferable because it becomes a non-aqueous electrolyte having excellent electrochemical stability. Further, a solvent in which a cyclic carbonate and a chain carbonate are mixed is preferable because it becomes a non-aqueous electrolyte having an excellent balance between viscosity and electric conductivity.

  Among the cyclic carbonates, ethylene carbonate and propylene carbonate having high dielectric constants are preferable. When graphite is used as the negative electrode active material, ethylene carbonate is particularly preferable. These cyclic carbonates may be used as a mixture of two or more.

  Among the chain carbonates, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate having low viscosity are preferable. These chain carbonates may be used as a mixture of two or more.

  The mixing ratio of the cyclic carbonate and the chain carbonate (cyclic carbonate: chain carbonate) is preferably from 1:99 to 99: 1 in terms of mass ratio. By being within such a range of the mixing ratio, the viscosity of the electrolytic solution can be suppressed low, and the degree of dissociation of the electrolyte can be increased, so that the conductivity of the electrolytic solution related to the charge / discharge characteristics of the battery can be increased. Can be. As a result, an electrolyte having good electrical conductivity in a range from room temperature to low temperature is obtained, so that the load characteristics of the battery from room temperature to low temperature can be improved. The mixing ratio is more preferably from 5:95 to 70:30, and even more preferably from 10:90 to 60:40.

  Examples of the electrolyte used in the present invention include a metal ion or a salt thereof, and a metal ion or a salt thereof belonging to Group 1 or 2 of the periodic table is preferable. The electrolyte is appropriately selected depending on the purpose of use of the electrolyte. Examples of the electrolyte include a lithium salt, a potassium salt, a sodium salt, a calcium salt, and a magnesium salt. A lithium salt is preferable because a lithium ion secondary battery having a large output can be obtained. When the nonaqueous electrolyte of the present invention is used as an electrolyte of a nonaqueous electrolyte for a lithium secondary battery, a lithium salt may be selected as a metal ion salt. The lithium salt is not particularly limited as long as it is a lithium salt usually used for an electrolyte of a non-aqueous electrolyte for a lithium secondary battery. For example, those described below are preferable.

(L-1) inorganic lithium _{salt: LiPF 6, LiBF 4, LiAsF} 6, LiSbF 6 , etc. of the inorganic fluoride _salts; LiAlCl ₄ Inorganic chloride salts, such as; LiClO _4, LiBrO _4, perhalogenate of LiIO ₄ such etc.

(L-2) Fluorine-containing organic lithium salt: perfluoroalkane sulfonate such as LiCF ₃ SO ₃ ; LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (FSO ₂ ) _{2 , LiN (CF 3 SO 2)} (C 4 F 9 SO 2) perfluoroalkanesulfonyl imide salts such as; _LiC (CF 3 _{SO 2)} perfluoroalkanesulfonyl methide salts of ₃ such; Li _[PF 5 (CF _{2 CF 2 CF 3)], Li} [PF 4 (CF 2 CF 2 CF 3) 2], Li [PF 3 (CF 2 CF 2 CF 3) 3], Li [PF 5 (CF 2 CF 2 CF 2 CF 3 _{)], Li [PF 4 (} CF 2 CF 2 CF 2 CF 3) 2], Li [PF 3 (CF 2 CF 2 CF 2 CF 3) 3] fluoroalkyl fluoride such as potash Acid salts, and the like.

  (L-3) Oxalato borate salt: lithium bis (oxalato) borate, lithium difluorooxalato borate and the like.

Of _{these, LiAlCl 4, LiBF 4, LiPF} 6, LiClO 4, LiAsF 6 and those from the group consisting of LiSbF ₆ of one or more members selected preferably because of its excellent electrical conductivity. One type of electrolyte may be used alone, or two or more types may be arbitrarily combined.

  The concentration of the electrolyte in the non-aqueous electrolyte used in the present invention is not particularly limited, but a preferable lower limit is 0.1 mol / L and a preferable upper limit is 2.0 mol / L. If the concentration of the electrolyte is less than 0.1 mol / L, the conductivity and the like of the non-aqueous electrolyte cannot be sufficiently ensured, and when used in a lithium ion secondary battery, the charge / discharge characteristics and the like are hindered. May cause damage. If the concentration of the electrolyte exceeds 2.0 mol / L, the viscosity increases, and the mobility of ions cannot be sufficiently secured. Therefore, the conductivity and the like of the nonaqueous electrolyte cannot be sufficiently secured. When used in an ion secondary battery, there is a possibility that the discharge characteristics and the charge characteristics may be affected. A more preferred lower limit of the concentration of the electrolyte is 0.5 mol / L, and a more preferred upper limit is 1.5 mol / L.

  The microporous sheet or film of the present invention is preferably used as a non-aqueous electrolyte secondary battery separator because it has good electrolyte permeability. This is because not only the fine particles made of polyarylene sulfide resin having a large number of carboxy groups are present on the inner wall surface of the pores of the microporous membrane, but also the particle size is a fraction of 10% or more of all the particles. It is considered that the presence of ultrafine particles of 100 nm or less increases the total specific surface area of the polyarylene sulfide resin particles and improves the wettability with the electrolytic solution.

  In the present invention, the terms sheet, film and film are not particularly strictly distinguished, but are used to clarify that any of them is included. , Films and membranes are to be interpreted as broadly as possible and these terms are intended to include what is termed a plate or plate as long as it has the features of the invention. When it is necessary to distinguish between a sheet and a film, the sheet is generally used when its thickness is 200 μm to 5 mm, and the film is usually used when its thickness is 5 to 200 μm according to a general interpretation. (See, for example, Polymer Dictionary edited by the Society of Polymer Science, Asakura Shoten, 1971).

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Measurement example) Melt viscosity of PPS resin (V6)
Using a flow tester ("CFT-500D type" manufactured by Shimadzu Corporation), the temperature / 300 ° C., the load is 1.96 MPa, and the ratio of the former to the latter of the orifice length and the orifice diameter is 10/1. The melt viscosity after holding for 6 minutes was measured using an orifice.

(Measurement Example) Melting Point of PPS Resin The temperature was raised from 50 ° C. to 350 ° C. at 20 ° C./min using a DSC apparatus manufactured by Perkin Elmer, and the endothermic peak temperature (Tm) which appeared when the polymer was melted was measured.

(Measurement Example) Determination of Carboxyl Group of PPS Resin After pressing the carboxy group of the PPS resin at 350 ° C., the film was quenched to form a film exhibiting amorphousness, and a Fourier transform infrared spectrometer (hereinafter “FT”) was used. -IR device "). It determined the relative intensity of the absorption of 1705 cm ^-1 for absorption of 630.6Cm ^-1 of infrared absorption spectrum, additional content of carboxyl group in the measurement sample using a calibration curve prepared by the method described later (hereinafter "carboxy Abbreviated as "total content of groups"). The content of the carboxy group is represented by the number of moles in 1 g of the resin composition, and its unit is represented by μmol / g. In addition, a calibration curve was prepared by adding a predetermined amount of 4-chlorophenylacetic acid to 3 g of PPS resin containing a carboxylate at a molecular end without performing acid treatment and mixing well, and then preparing a film in the same manner as described above. And an FT-IR apparatus, and a calibration curve was prepared in which the relative intensity ratio of the absorption to the carboxy group content was plotted.

(Measurement Example) Measurement of PPS Resin Particles The cross section of the pellet-shaped polyphenylene sulfide resin particle dispersion (hereinafter, PPS resin dispersion) obtained in the example and the cross section of the sheet test piece were measured with an SEM apparatus (JEOL). It was measured by "JSM-6360A" manufactured by Co., Ltd.). Approximately 300 particles made of PPS resin were randomly selected from the obtained images, and the particle diameter and the number average particle diameter of the particles were calculated. However, the particle diameter was calculated as a circle equivalent diameter.

(Measurement example) MFR and MI of polyolefin
The melt flow rate (MFR) measured according to ASTM D1238 (190 ° C., load 2.16 kgf, orifice diameter 2 mm) was measured (g / 10 minutes).

Example 1 Production of PPS Particle Dispersion Polyarylene sulfide resin (“DIC.PPS” manufactured by DIC Corporation, melting point 278 ° C., non-NT index 1.13, melt viscosity at 300 ° C.) in the ratio described in Table 1. (V6) 150 (Pa · s), carboxy group content 45 μmol / g, hereinafter referred to as “PPS (a1)”) and “BF-E” manufactured by Sumitomo Chemical Co., Ltd. (ethylene / glycidyl methacrylate (88/12 mass%) ) A copolymer, MFR3 (g / 10 minutes), hereinafter referred to as “PO (b1)”) was charged into a tumbler and uniformly mixed to obtain a compounding material.
Thereafter, the compounded material was charged into a vented twin screw extruder “TEX-30α” manufactured by Nippon Steel Works Co., Ltd. and melt-kneaded (resin component discharge amount 20 kg / hr, screw rotation speed 350 rpm, resin component discharge amount 0.1 mm). After 057 (kg / hr / rpm) at a cylinder setting resin temperature of 320 ° C.), the mixture was extruded in a strand shape and subsequently cut to obtain a pellet-shaped PPS particle dispersion (1).
FIG. 1 shows an SEM photograph of the PPS particle dispersion obtained in Example 1. FIG. 2 shows the particle size distribution.

(Example 2) Production of PPS particle dispersion In addition to PPS (a1) and PO (b1), polyethylene ("High Wax 410P" manufactured by Mitsui Chemicals, Inc., molecular weight 4000, hereinafter referred to as "PO (b2)") Was added in the proportions shown in Table 1 to obtain a PPS particle dispersion (2) in the same manner as in Example 1.

Example 3 Production of PPS Particle Dispersion Instead of PPS (a1), a polyarylene sulfide resin (“DIC.PPS” manufactured by DIC Corporation, melting point 280 ° C., non-NT index 1.90, melt viscosity at 300 ° C.) (V6) A PPS particle dispersion (3) was prepared in the same manner as in Example 1 except that 1500 (Pa · s) and a carboxy group content of 2 μmol / g, hereinafter referred to as “PPS (a2)” were used. Obtained.

(Examples 4 and 5) Production of PPS particle dispersion A PPS particle dispersion (4) was prepared in the same manner as in Example 1 except that the ratio of PPS (a1) and PO (b1) was as shown in Table 1. (5) was obtained.

Comparative Example 1 Production of Comparative PPS Particle Dispersion Instead of PPS (a1), a polyarylene sulfide resin (“DIC.PPS” manufactured by DIC Corporation, melting point 278 ° C., non-NT index 1.07, 300 ° C.) Except for using a melt viscosity (V6) of 15 (Pa · s) and a carboxy group content of 60 μmol / g, hereinafter referred to as “PPS (a3)”, a resin particle dispersion (6 ) Got.

(Comparative Example 2) Production of Comparative PPS Particle Dispersion Resin particle dispersion (7) was prepared in the same manner as in Example 1 except that the ratio of PPS (a1) and PO (b1) was as shown in Table 1. Obtained.

However, the composition ratio in the table is based on parts by mass.
* 1 Polyolefin ("BF-E" manufactured by Sumitomo Chemical Co., Ltd.) dispersed as particles in a PPS resin matrix.

(Measurement Example 5) Tensile elastic modulus and tensile elongation at break In accordance with ASTM D-638, an ASTM No. 4 dumbbell was prepared for the pellets obtained in Examples 6 and 7 and Comparative Examples 4 to 10 at 23 ° C. The tensile modulus (MPa) and tensile elongation at break (%) at 120 ° C. were measured. The results are shown in Tables 2 and 3.

(Example 6) Manufacture of test piece The above-mentioned PPS particle dispersion (1) and polyethylene (“Sunfine LH-311” Asahi Kasei Chemicals Corporation) MFR = 18 g / 10 min. (Described as (c1))) into a vented twin-screw extruder “TEX-30α” manufactured by Nippon Steel Works, Ltd., and melt-kneaded (resin component discharge rate 15 kg / hr, screw rotation speed 200 rpm), resin component A melt-kneaded product was prepared at a discharge rate of 0.075 (kg / hr / rpm) at a cylinder setting resin temperature of 230 ° C., and then extruded into strands to produce pellets (1).

(Example 7) Production of test piece A pellet (2) was produced in the same manner as in Example 6, except that the PPS particle dispersion (2) was used instead of the PPS particle dispersion (1).

(Comparative Example 4) Production of a comparative test piece Pellets (3) in the same manner as in Example 6 except that a PPS particle dispersion (7) for comparison was used instead of the PPS particle dispersion (1). Was manufactured.

(Comparative Example 5) Production of a comparative test piece Pellets (4) in the same manner as in Example 7 except that a PPS particle dispersion (8) for comparison was used instead of the PPS particle dispersion (1). Was manufactured.

(Comparative Example 6) Production of a comparative test piece Pellets (5) were produced in the same manner as in Example 7 except that the set resin temperature of 230 ° C during melt-kneading was changed to 320 ° C.

However, the composition ratio in the table is based on parts by mass.

(Comparative Example 7) Manufacture of a comparative test piece PPS (a1), PO (b1), and PO (c1) were mixed at the ratios shown in Table 3 with a vented twin-screw extruder manufactured by Japan Steel Works, Ltd. The resin was charged into “TEX-30α”, melt-kneaded (resin component discharge amount 15 kg / hr, screw rotation speed 200 rpm), resin component discharge amount 0.075 (kg / hr / rpm), and set resin temperature 230 ° C. ) To prepare a melt-kneaded product, which was extruded into strands to produce pellets (6).

(Comparative Example 8) Production of a test piece for comparison A pellet (7) was produced in the same manner as in Comparative Example 7, except that the set resin temperature of 230 ° C during melt-kneading was changed to 320 ° C.

(Comparative Example 9) Production of a comparative test piece Pellets were produced in the same manner as in Comparative Example 7 except that PPS (a1), PO (b1), and PO (c1) were set to the ratios shown in Table 3. (8) was obtained.

(Comparative Example 10) Production of Comparative Test Piece A pellet (9) was obtained in the same manner as in Comparative Example 7, except that only PO (c1) was used.

However, the composition ratio in the table is based on parts by mass.
* 3 Measurement not possible

(Measurement Example 6) Heat Shrinkage The sheet test pieces obtained in the following Examples 8 and 9 and Comparative Examples 11 to 17 were cut into 50 mm x 50 mm, and JIS-K7133 "Plastic film and sheet-Measurement of dimensional change upon heating" Method ", the heat shrinkage was measured (average of the vertical and horizontal shrinkage after standing at 150 ° C. for 10 minutes). The results are shown in Tables 4 and 5.

(Example 8) Manufacture of sheet At the ratios shown in Table 4, the above PPS particle dispersion (1) and polyethylene (Asahi Kasei Chemicals Corporation "Sunfine LH-311" MFR = 18 g / 10 min, hereinafter referred to as "PO ( c1))) into a twin-screw extruder "TEX-30α" manufactured by Nippon Steel Works, Ltd., melt-kneaded (resin component discharge amount 15 kg / hr, screw rotation speed 200 rpm), resin component discharge An amount of 0.075 (kg / hr / rpm) was set at a cylinder setting resin temperature of 230 ° C. to prepare a melt-kneaded product. Subsequently, T-die extrusion molding was performed so as to have a film thickness of 0.1 (mm), and the sheet was cooled while being taken up by a cooling roll adjusted to 80 ° C. to produce a sheet test piece (1).

(Example 9) Production of sheet A sheet test piece (2) was produced in the same manner as in Example 8, except that the PPS particle dispersion (2) was used instead of the PPS particle dispersion (1).

(Comparative Example 11) Production of Comparative Sheet A sheet test piece (3) was prepared in the same manner as in Example 8 except that a PPS particle dispersion (7) for comparison was used instead of the PPS particle dispersion (1). ) Manufactured.

(Comparative Example 12) Production of Comparative Sheet A sheet test piece (4) was prepared in the same manner as in Example 8 except that a PPS particle dispersion (8) for comparison was used instead of the PPS particle dispersion (1). ) Manufactured.

(Comparative Example 13) Production of Comparative Sheet A sheet test piece (5) was produced in the same manner as in Example 8, except that the set resin temperature of 230 ° C during melt-kneading was 320 ° C.

However, the composition ratio in the table is based on parts by mass.
* 2 Coarse particles composed of a dispersion in which polyolefin (PO (b1)) is dispersed as particles in a matrix composed of a PPS resin, and polyethylene (PO (c1)) dispersed as a matrix.

(Comparative Example 14) Production of comparative sheet PPS (a1), PO (b1), and PO (c1) were mixed at the ratios shown in Table 5 with a vented twin-screw extruder manufactured by Nippon Steel Works, Ltd. TEX-30α ”, melt-kneading (resin component discharge rate 15 kg / hr, screw rotation speed 200 rpm), resin component discharge rate 0.075 (kg / hr / rpm) at a set resin temperature of 230 ° C.) Thus, a melt-kneaded product was prepared. Subsequently, T-die extrusion molding was performed so as to have a film thickness of 0.1 mm, and the resultant was cooled while being taken up by a cooling roll adjusted to a temperature of 80 ° C., thereby producing a sheet test piece (6).

(Comparative Example 15) Production of Comparative Sheet A sheet test piece (7) was produced in the same manner as in Comparative Example 14 except that the set resin temperature of 230 ° C during melt-kneading was changed to 320 ° C.

(Comparative Example 16) Production of Comparative Sheet Sheet test was performed in the same manner as in Comparative Example 14 except that the ratios of PPS (a1), PO (b1), and PO (c1) were set as shown in Table 3. A piece (8) was obtained.

(Comparative Example 17) Production of Comparative Sheet A sheet test piece (9) was obtained in the same manner as in Comparative Example 14, except that only PO (c1) was used.

However, the composition ratio in the table is based on parts by mass.
* 3 Measurement not possible

(Example 10, Comparative Example 18) Production of microporous sheet for separator At the ratio shown in Table 6, the above PPS particle dispersion (1) or (7) and polyethylene ("HI-ZEX 5305EP" manufactured by Prime Polymer Co., Ltd.) , MI = 0.8 (g / 10 min), hereinafter referred to as “PO (c2)”) by a tumbler to obtain a compounded material.

  Thereafter, the compounded material was charged into a twin-screw extruder (“TEX-30α” manufactured by Nippon Steel Works, Ltd.), melt-kneaded (resin component discharge amount 15 kg / hr, screw rotation speed 200 rpm), resin component discharge amount 0. 0.075 (kg / hr / rpm) at a cylinder setting resin temperature of 230 ° C.) to prepare a melt-kneaded product. Further, a pore forming agent (a mixture of liquid paraffin and bis (2-ethylhexyl) phthalate in equal amounts) was added from a side feeder to obtain a resin composition. Subsequently, the obtained resin composition was die-extruded and cooled on a roll whose surface was maintained at 80 ° C., to produce a sheet material having a thickness of 0.3 mm.

This sheet material was stretched 3 × 3 times at 120 ° C. with a batch-type biaxial stretching machine to obtain a biaxially stretched film having a thickness of 0.03 mm.
The obtained biaxially stretched film was heat-set at 125 ° C. for 3 minutes while being held by a tenter stretching machine.

  After fixing the heat-set biaxially stretched film to a glass frame of 20 cm × 20 cm, the film is immersed for 1 hour in a pore-forming agent removing tank filled with methylene chloride adjusted to 25 ° C. to remove the pore-forming agent. Thus, a microporous sheet having a thickness of 0.03 mm was manufactured, and the following measurement was performed.

(Measurement example) Melt-down resistance The microporous membrane was exposed to a hot-air dryer set at 120 ° C for 1 minute, and measured in accordance with JIS-K7133 “Plastic-Film and Sheet-Measurement Method of Dimensional Change by Heating”. The heat shrinkage of the microporous membrane of 0.03 mm was measured. The microporous film was measured at 10 points, the average value was determined, and the meltdown resistance was evaluated according to the following criteria.
The average value of the heat shrinkage is 0% or more and 2% or less ... ◎ (Excellent meltdown resistance)
The average value of the heat shrinkage ratio is more than 2% and 3% or less ... ○ (Excellent meltdown resistance)
The average value of the heat shrinkage is more than 3% and 4% or less ... △ (melt down resistance is poor)
Average value of thermal shrinkage exceeds 4% ・ ・ ・ × (No meltdown resistance)

(Measurement example) Gurley air permeability The Gurley air permeability of the porous membrane was measured in accordance with JIS-P8117 "Paper and paperboard-Air permeability and air resistance test method (intermediate region)-Gurley method".

(Measurement Example) Shutdown Temperature The microporous membrane was exposed to a hot air dryer set at a predetermined temperature for 1 minute, and the temperature at which the Gurley value reached 5000 seconds / 100 ml or more was defined as the shutdown temperature.

* The numerical values related to the mixing ratio of each composition component in the table represent parts by mass.

Claims (8)

Particles of the polyarylene sulfide resin (A) having a melt viscosity (V6) of 100 to 2000 (Pa · s) measured at 300 ° C. are contained in the functionalized polyolefin (B1) or the functionalized polyolefin (B1). A) a polyarylene sulfide resin particle dispersion dispersed in a polyolefin resin composition (B) containing
In the particles, the proportion of particles having a particle diameter of 100 nm or less in all particles is 10% or more in fractions,
The ratio of the polyolefin (B1) having a functional group in the polyolefin resin composition (B) is in the range of 80 to 100% by mass;
The functional group of the polyolefin (B1) is at least one selected from the group consisting of an epoxy group, an amino group, a hydroxy group, a carboxyl group, a mercapto group, an isocyanate group, a vinyl group, an acid anhydride group and an ester group. ,
A polyarylene sulfide resin particle dispersion comprising:   The polyarylene sulfide resin particle dispersion according to claim 1, wherein the particles have an average particle diameter (D50) in the range of 0.1 to 1 (μm).   The polyarylene sulfide resin particle dispersion is prepared by mixing the polyarylene sulfide resin (A) in a range of 70 to 50 parts by mass and the polyolefin resin composition (B) in a range of 30 to 50 parts by mass with a polyarylene sulfide resin ( The polyarylene sulfide resin particle dispersion according to claim 1, which is obtained by melt-kneading at a temperature higher than the melting point of A). Particles comprising a polyarylene sulfide resin (A) having a melt viscosity (V6) measured at 300 ° C. in the range of 100 to 2000 (Pa · s) are a polyolefin having a functional group (B1) or a polyolefin having a functional group (B1). The polyarylene sulfide resin particle dispersion, wherein the particles are dispersed in a polyolefin resin composition (B) containing: The method of manufacturing
Melting and kneading the polyarylene sulfide resin (A) in a range of 70 to 50 parts by mass and the polyolefin resin composition (B) in a range of 30 to 50 parts by mass at a temperature higher than the melting point of the polyarylene sulfide resin. ,
The ratio of the polyolefin (B1) having a functional group in the polyolefin resin composition (B) is in the range of 80 to 100% by mass;
The functional group of the polyolefin (B1) having the functional group is at least selected from the group consisting of an epoxy group, an amino group, a hydroxy group, a carboxyl group, a mercapto group, an isocyanate group, a vinyl group, an acid anhydride group and an ester group. One kind,
A method for producing a polyarylene sulfide resin particle dispersion, comprising: A polyarylene sulfide resin particle dispersion of 10 to 70 parts by mass and a thermoplastic resin (C) of 30 to 90 parts by mass are mixed with a polyolefin (B1) having a functional group lower than the melting point of the polyarylene sulfide resin and having a functional group. Melt kneading at a temperature higher than the melting point of any of the polyolefin resin composition (B) containing the polyolefin having a group (B1) and the thermoplastic resin (C),
Particles composed of the polyarylene sulfide resin (A) having a melt viscosity (V6) of 100 to 2000 (Pa · s) measured at 300 ° C. are the polyolefin (B1) or the polyolefin resin composition (B) and the polyarylene. It is dispersed in a resin composition containing a thermoplastic resin (C) having a lower melting point than a sulfide resin,
And a method for producing a thermoplastic resin composition in which the particles have a fraction of particles having a particle size of 100 nm or less in all particles being 10% or more in fractions,
The polyarylene sulfide resin particle dispersion,
Particles of the polyarylene sulfide resin (A) having a melt viscosity (V6) of 100 to 2000 (Pa · s) measured at 300 ° C. are contained in the functionalized polyolefin (B1) or the functionalized polyolefin (B1). A) a polyarylene sulfide resin particle dispersion dispersed in a polyolefin resin composition (B) containing
In the particles, the proportion of particles having a particle diameter of 100 nm or less in all particles is 10% or more in fractions,
The functional group of the polyolefin (B1) having the functional group is at least selected from the group consisting of an epoxy group, an amino group, a hydroxy group, a carboxyl group, a mercapto group, an isocyanate group, a vinyl group, an acid anhydride group and an ester group. One kind,
The thermoplastic resin (C) is at least one selected from the group consisting of polyamide, polyester, polycarbonate, polystyrene, ABS and polyolefin;
A method for producing a thermoplastic resin composition, comprising: A polyarylene sulfide resin particle dispersion 10 to 70 parts by weight, and a thermoplastic resin (C) 30 to 90 parts by weight, lower than the melting point of the polyarylene sulfide resin and a polyolefin having a functional group (B1) or A step of obtaining a thermoplastic resin composition by melt-kneading the polyolefin resin composition (B) containing the functional group-containing polyolefin (B1) and the thermoplastic resin (C) in a temperature range higher than the melting point of any of the above. (1),
Sheeting the thermoplastic resin composition heated to a temperature lower than the melting point of the polyarylene sulfide resin and higher than the melting point of any of the polyolefin resin composition (B) and the thermoplastic resin (C); The film is formed, and the particles comprising the polyarylene sulfide resin (A) are dispersed in a resin composition containing the polyolefin resin composition (B) and the thermoplastic resin (C), and the particles are: A process for obtaining a sheet or film in which the ratio of particles having a particle size of 100 nm or less to all particles is 10% or more in fractions (2),
The polyarylene sulfide resin particle dispersion,
Particles of the polyarylene sulfide resin (A) having a melt viscosity (V6) of 100 to 2000 (Pa · s) measured at 300 ° C. are contained in the functionalized polyolefin (B1) or the functionalized polyolefin (B1). A) a polyarylene sulfide resin particle dispersion dispersed in a polyolefin resin composition (B) containing
In the particles, the proportion of particles having a particle diameter of 100 nm or less in all particles is 10% or more in fractions,
The functional group of the polyolefin (B1) having the functional group is at least selected from the group consisting of an epoxy group, an amino group, a hydroxy group, a carboxyl group, a mercapto group, an isocyanate group, a vinyl group, an acid anhydride group and an ester group. One kind,
The method for producing a sheet or film, wherein the thermoplastic resin (C) is at least one selected from the group consisting of polyamide, polyester, polycarbonate, polystyrene, ABS and polyolefin .   In the step (1), in addition to the polyarylene sulfide resin particle dispersion and the thermoplastic resin (C), a pore forming agent (D) or a β crystal nucleating agent (E) is further kneaded, and ) And the step (2), wherein the sheet or film obtained in the step (2) further comprises a step (3) of making the sheet or film porous, the sheet or film being a microporous sheet. Or a method for producing a film.   In the step (1), the pore-forming agent (D) is used with respect to a total of 100 parts by mass of the particles composed of the polyarylene sulfide resin (A), the polyolefin resin composition (B), and the thermoplastic resin (C). Is in the range of 25 to 250 parts by mass, or the β crystal nucleating agent is 0.0001 to 10 parts by mass based on 100 parts by mass of the total of the polyolefin resin composition (B) and the thermoplastic resin (C). The method for producing a sheet or film according to claim 7, which is in a range of parts by mass.