JP5196908B2 - Laminated porous film, battery separator and battery using the same - Google Patents

Description

  The present invention relates to a laminated porous film, and can be used as a packaging product, sanitary product, livestock product, agricultural product, building product, medical product, separation membrane, light diffusing plate, battery separator, and particularly as a nonaqueous electrolyte battery separator. It can be used suitably.

Secondary batteries are widely used as power sources for portable devices such as OA, FA, household electric appliances and communication devices. In particular, portable devices using lithium ion secondary batteries are increasing because they have a high volumetric efficiency when mounted on devices, leading to a reduction in size and weight of the devices.
On the other hand, large-sized secondary batteries are being researched and developed in many fields related to energy / environmental issues, including road leveling, UPS, and electric vehicles, and are excellent in large capacity, high output, high voltage, and long-term storage. Therefore, the use of lithium ion secondary batteries, which are a kind of non-aqueous electrolyte secondary battery, is expanding.

The working voltage of a lithium ion secondary battery is usually designed with an upper limit of 4.1V to 4.2V. At such a high voltage, the aqueous solution causes electrolysis and cannot be used as an electrolyte. Therefore, so-called non-aqueous electrolytes using organic solvents are used as electrolytes that can withstand high voltages.
As the solvent for the non-aqueous electrolyte, a high dielectric constant organic solvent capable of making more lithium ions exist is used, and organic carbonates such as polypropylene carbonate and ethylene carbonate are mainly used as the high dielectric constant organic solvent. It is used. As a supporting electrolyte that becomes a lithium ion source in the solvent, a highly reactive electrolyte such as lithium hexafluorophosphate is dissolved in the solvent and used.

  In the lithium ion secondary battery, a separator is interposed between the positive electrode and the negative electrode from the viewpoint of preventing an internal short circuit. Of course, the separator is required to have insulating properties due to its role. Moreover, it is necessary to have a microporous structure in order to provide air permeability as a lithium ion passage and a function of diffusing and holding the electrolyte. In order to satisfy these requirements, a porous film is used as a separator.

With the recent increase in battery capacity, the importance of battery safety has increased.
A characteristic that contributes to the safety of battery separators is a shutdown characteristic (hereinafter referred to as SD characteristic). This SD characteristic is a function that can prevent the subsequent increase in temperature inside the battery because the micropores are closed when the temperature is about 100 ° C. to 150 ° C., and as a result, ion conduction inside the battery is blocked. When used as a battery separator, it is necessary to have this SD characteristic.

  Another characteristic that contributes to safety is breakdown characteristics (hereinafter referred to as BD characteristics). This BD characteristic is a function in which heat generation does not stop due to the development of the SD characteristic, and the film does not break even when the temperature is higher (200 ° C. or higher) and keeps the positive electrode and the negative electrode separated. If it has BD characteristics, insulation can be maintained even at high temperatures, and a wide range of short-circuits between electrodes can be prevented, thereby preventing accidents such as ignition due to abnormal heat generation of the battery. Therefore, when used as a battery separator, it is preferable that this BD characteristic is also provided, and the breakdown temperature is preferably higher.

In response to such a demand, Japanese Patent No. 2883726 (Patent Document 1) is characterized in that a laminated film of polyethylene and polypropylene is made porous by changing the temperature in one axial direction and stretching in two stages. A separator manufacturing method has been proposed.
However, this manufacturing method requires strict control of manufacturing conditions, and it is difficult to say that productivity is good. For example, when creating a laminated film before making it porous, film formation is performed while controlling the higher order structure with a high draft ratio, but it is very difficult to form a stable film with such a high draft ratio. Have difficulty. In addition, in order to develop a porous structure, it is necessary to perform multistage stretching at two stages, a low temperature region and a high temperature region, at a low stretching speed, and the stretching speed is greatly limited, resulting in extremely poor productivity. .
Furthermore, the separator manufactured by the manufacturing method is very weak against tearing in the same direction as the stretching direction, and there is a problem that a tear is easily generated in the stretching direction.

  On the other hand, as a method for obtaining a porous film by stretching a polypropylene sheet containing a large amount of β crystals, which is one of crystal forms, in order to increase the permeability of the porous film, Japanese Patent No. 1953202 (Patent Document 2), Patent Japanese Patent No. 2509030 (Patent Document 3), Japanese Patent No. 3443934 (Patent Document 4), and the like have been proposed.

These polypropylene porous films are superior to polyethylene porous films in BD characteristics because of the high crystal melting temperature of polypropylene. However, since the above characteristics are adversely affected and the SD characteristics cannot be exhibited at all, using these porous films as battery separators has a problem in securing battery safety. In addition, with the recent increase in energy density of batteries, it has become difficult to say that heat resistance is sufficient for polypropylene, so there is room for improvement in the breakdown temperature to be higher.
Thus, there is a demand for a porous film that can exhibit BD characteristics at a higher temperature than conventional polypropylene porous films and can also exhibit SD characteristics.

Japanese Patent No. 2883726 Japanese Patent No. 1953202 Japanese Patent No. 2509030 Japanese Patent No. 3443934

  The present invention has been made in view of the above problems, and has a porous structure with sufficient strength while maintaining strength, and has better breakdown (BD) characteristics than conventional polypropylene porous films. And providing a laminated porous film that can exhibit shutdown (SD) characteristics.

In order to solve the above problems, the present invention is a laminated porous film comprising at least a first layer to a third layer of porous layers,
The first layer is a layer made of a composition containing a β crystal nucleating agent in a polypropylene resin,
The second layer is a layer made of a composition having a peak value of crystal melting temperature higher than a peak value of crystal melting temperature of the composition of the first layer,
The third layer is a layer made of a composition having a peak value of crystal melting temperature lower than a peak value of crystal melting temperature of the composition of the first layer,
The first layer micropores by applying the extension Shin is formed, also the second and third layers filler method, phase separation method, an extraction method, a chemical treatment method, an irradiation etching method, is selected from foaming Micropores are formed by applying one or more methods , and
The present invention provides a laminated porous film characterized by having β activity and / or β crystal generation ability.

  In the present invention, since the first layer is a layer made of a composition containing a polypropylene resin (hereinafter referred to as (A)), strength can be imparted to the laminated porous film, and the second layer is the first layer. Since it forms from the composition which has the peak value of the crystal melting temperature higher than the peak value of the crystal melting temperature of the composition of a layer, the 2nd layer can provide heat resistance. Furthermore, since the third layer is formed of a composition having a peak value of the crystal melting temperature lower than the peak value of the crystal melting temperature of the composition of the first layer, the third layer is porous at a temperature lower than that of the first layer. Can be closed.

The laminated porous film of the present invention has β activity and / or β crystal generation ability, and a β crystal nucleating agent is blended in the composition of the first layer. Both the β activity and β crystal generation power, the polypropylene resin was produced the β crystal in the membrane material before stretching can be considered as one indicator of the polypropylene in the membrane material before stretching If the β-type resin produces β crystals, fine pores are formed by subsequent stretching, so that a layer having air permeability characteristics can be obtained.
The presence or absence of the “β activity” is determined to have β activity when the crystal melting peak temperature derived from the β crystal is detected by a differential scanning calorimeter described later.
In addition, the presence or absence of the “β crystal formation force” indicates that the β crystal formation force is present when a diffraction peak derived from the β crystal is detected by measurement of the β crystal formation force using an X-ray analyzer described later. Judging.
When the laminated porous film of the present invention is composed of only the first layer, the second layer, and the third layer, the β activity and / or the β crystal generation force are obtained when another porous layer is laminated. In either case, the measurement is performed in the state of a laminated porous film.

As described above , at least the first layer of the compositions of the first layer, the second layer, and the third layer is blended with a β crystal nucleating agent in the polypropylene resin (A), and the β activity and / or the β It is assumed to have a crystal generating force. The amount of the β crystal nucleating agent is preferably 0.0001 to 5.0 parts by weight with respect to the polypropylene resin (A) 100 parts by mass of.

The second layer includes a thermoplastic resin (hereinafter referred to as (B)) having a peak value of crystal melting temperature of 200 ° C. or higher, and is a heat-resistant layer having a breakdown temperature for breaking the film of 200 ° C. or higher. Is preferred.
When the composition of the second layer contains a thermoplastic resin (B) having a peak value of crystal melting temperature of 200 ° C. or higher, it exhibits breakdown characteristics at a high temperature of 200 ° C. or higher when used as a battery separator. The layer can be made to be extremely heat resistant. The upper limit of the crystal melting peak temperature of the resin (B) is not particularly limited, but is preferably 400 ° C. or lower.
The thermoplastic resin (B) having a peak value of the crystal melting temperature of the second layer of 200 ° C. or higher is a resin different from the polypropylene resin (A) and has a differential scanning calorific value in accordance with JIS K7121. When the temperature is raised from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min using a meter, the peak value of the crystal melting temperature detected is 200 ° C. or higher. Especially, it is preferable that the said resin (B) is at least 1 sort (s) chosen from the group which consists of a polyester-type resin, a polystyrene-type resin, a fluorine-type resin, and a polymethylpentene resin.

On the other hand, the third layer contains a thermoplastic resin (hereinafter referred to as (C)) having a peak value of crystal melting temperature of 100 ° C. or higher and 150 ° C. or lower, so that the pores are closed at 100 ° C. or higher and 150 ° C. or lower. It is preferable that the shutdown layer has a function to be performed.
When the composition of the third layer includes the thermoplastic resin (C) having a peak value of the crystal melting temperature of 100 ° C. or higher and 150 ° C. or lower, the temperature range is particularly suitable when used as a battery separator. It can be set as the layer which can exhibit a shutdown characteristic in the range of 150 degreeC or more.
The thermoplastic resin (C) having a peak value of the crystal melting temperature of the third layer of 100 ° C. or more and 150 ° C. or less is a resin different from the polypropylene resin (A) and has a differential according to JIS K7121. When the temperature is raised from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./minute using a scanning calorimeter, the detected peak value of the crystal melting temperature is 100 ° C. or more and 150 ° C. or less. Especially, it is preferable that the said resin (C) is a polyethylene-type resin.

  Moreover, it is preferable that the said 2nd layer and / or the said 3rd layer contain the filler.

The laminated porous film of the present invention preferably has an air permeation resistance measured according to JIS P8117 of 1 to 10000 seconds / 100 ml.
Further, according to Japanese Agricultural Standards Notification No. 1019, it is preferable that the pin penetration strength measured under the conditions of a pin diameter of 1.0 mm, a tip portion 0.5R, and a pin penetration rate of 300 mm / min is 1.5N.

  The present invention includes a battery separator having a gas permeability resistance of 5 to 3000 seconds / 100 ml measured in accordance with JIS P8117, and a highly safe battery in which the separator is incorporated. providing.

The laminated porous film of the present invention comprises a first layer composed of a composition containing a β crystal nucleating agent in a polypropylene resin , a peak value of a crystal melting temperature higher than the peak value of the crystal melting temperature of the composition of the first layer. And a third layer composed of a composition having a peak value of the crystal melting temperature lower than the peak value of the crystal melting temperature of the composition of the first layer. The second layer has higher heat resistance than the conventional polypropylene porous film, and the three layers have shutdown characteristics. Therefore, when the laminated porous film is used as a battery separator, it can have both shutdown characteristics and breakdown characteristics, and can be excellent in strength and heat resistance.
In addition, the laminated porous film of the present invention has β activity and / or β crystal generation power, and is excellent in mechanical strength such as pin puncture strength and tear strength while ensuring sufficient communication. It is also excellent from the viewpoint of structure maintenance and impact resistance.
As described above, the laminated porous film of the present invention has excellent air permeability, heat resistance and strength, is excellent in both shutdown characteristics and breakdown characteristics, and is useful for battery separators.
Furthermore, the laminated porous film of the present invention does not require strict control of manufacturing conditions, and can be produced easily and efficiently.

Hereinafter, embodiments of the laminated porous film of the present invention will be described in detail.
The laminated porous film of the present embodiment is a laminated porous film provided with at least three porous layers of a first layer, a second layer, and a third layer.
The first layer is a layer made of a composition containing a polypropylene resin, and the second layer is a composition having a peak value of the crystal melting temperature higher than the peak value of the crystal melting temperature of the composition of the first layer. The third layer is a layer made of a composition having a peak value of crystal melting temperature lower than the peak value of crystal melting temperature of the composition of the first layer, and the laminated porous film is It is characterized by having β activity and / or β crystal forming power.

The laminated porous film of the present invention is characterized by having at least one of the β activity and the β crystal generation force.
Both β activity and β crystal forming power can be regarded as one index indicating that the polypropylene resin has generated β crystals in the film-like material before stretching. If the polypropylene-based resin in the film-like material before stretching produces β crystals, fine pores are formed by subsequent stretching, and thus a laminated porous film having air permeability characteristics can be obtained.

The presence or absence of β activity of the laminated porous film can be determined by conducting a differential thermal analysis of the laminated porous film using a differential scanning calorimeter and detecting a crystal melting peak temperature derived from β crystals of polypropylene resin. Judgment is based on no.
Specifically, the laminated porous film is heated at a heating rate of 10 ° C./min from 25 ° C. to 240 ° C. for 1 minute with a differential scanning calorimeter, and then cooled from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C. / When the temperature is lowered for 1 minute and held for 1 minute, and when the temperature is raised again from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min, the crystal melting peak temperature (Tmβ) derived from the β crystal of the polypropylene resin is detected. In that case, it is determined to have β activity.

In addition, the β activity of the laminated porous film is calculated by the following formula using the heat of crystal melting derived from the α crystal of the polypropylene resin (ΔHmα) and the heat of crystal melting derived from the β crystal (ΔHmβ). Yes.
β activity (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100
For example, when the polypropylene resin is homopolypropylene, the amount of heat of crystal melting derived from the β crystal (ΔHmβ) detected mainly in the range of 145 ° C. or higher and lower than 160 ° C., and mainly detected at 160 ° C. or higher and 175 ° C. or lower. It can be calculated from the heat of crystal melting (ΔHmα) derived from the α crystal. Further, for example, in the case of random polypropylene copolymerized with 1 to 4 mol% of ethylene, the crystal melting heat amount (ΔHmβ) derived from the β crystal detected mainly in the range of 120 ° C. or more and less than 140 ° C., and mainly 140 It can be calculated from the crystal melting calorie (ΔHmα) derived from the α crystal detected in the range of from 0 ° C. to 165 ° C.

The β activity of the laminated porous film is preferably large, and the β activity is preferably 20% or more. More preferably, it is 40% or more, and particularly preferably 60% or more. If the laminated porous film has a β activity of 20% or more, it indicates that a large amount of β crystals of polypropylene resin can be produced in the film-like material before stretching, and fine and uniform pores are formed by stretching. Many layers are formed, and as a result, a laminated porous film having high mechanical strength and excellent air permeability can be obtained.
The upper limit of β activity is not particularly limited, but the higher the β activity, the more effective the effect is obtained.

The presence or absence of the β crystal generation force is determined by a diffraction profile obtained by wide-angle X-ray measurement of a laminated porous film subjected to a specific heat treatment.
Specifically, wide-angle X-ray measurement was performed on a laminated porous film that was heat-treated at 170 ° C. to 190 ° C., which is a temperature exceeding the melting point of the polypropylene resin (A), and slowly cooled to produce and grow β crystals. When the diffraction peak derived from the (300) plane of the β-crystal of the polypropylene resin is detected in the range of 2θ = 16.0 ° to 16.5 °, it is determined that there is a β-crystal forming power.
Details regarding the β crystal structure and wide angle X-ray diffraction of polypropylene resins can be found in Macromol. Chem. 187, 643-652 (1986), Prog. Polym. Sci. Vol. 16, 361-404 (1991), Macromol. Symp. 89, 499-511 (1995), Macromol. Chem. 75, 134 (1964), and references cited therein. A detailed evaluation method of the β crystal forming power will be described in the examples described later.

As described above, to obtain the β activity and / or β crystal generation power of the product layer porous film, before Symbol the β activity and / or β crystal produced by the addition of β-crystal nucleating agent in the composition of the first layer Gaining power . By adding a β crystal nucleating agent, it is possible to promote the generation of β crystals of polypropylene resin more uniformly and efficiently, and a laminated porous layer having a porous layer having β activity and / or β crystal generation ability Can be obtained.

Next, each layer will be described in detail.
[Explanation of the first layer]
The first layer is a porous layer made of a composition containing a polypropylene resin (A) having a large number of fine pores communicating in the thickness direction, and the polypropylene resin (A) is preferably the main component. Specifically, positive total mass of the polypropylene resin and β-crystal nucleating agent is 70 mass% or more relative to the total weight of the first layer, preferably 80 mass% or more, even more preferably accounts for 90 mass% or more.

In the present invention, beta crystal nucleating agent, especially formulated in the composition of the first layer, that are blended with polypropylene resin (A). The ratio of the β crystal nucleating agent to be added to the polypropylene resin (A) needs to be appropriately adjusted depending on the type of the β crystal nucleating agent or the composition of the polypropylene resin, but with respect to 100 parts by mass of the polypropylene resin. The β crystal nucleating agent is preferably 0.0001 to 5.0 parts by mass. 0.001-3.0 mass parts is more preferable, and 0.01-1.0 mass part is still more preferable. If it is 0.0001 part by mass or more, β-crystals of polypropylene resin can be sufficiently produced and grown during production, and sufficient β-activity and / or β-crystal-forming power can be secured even when used as a separator. Desired air permeation performance can be obtained. The addition of 5.0 parts by mass or less is preferable because it is economically advantageous and there is no β crystal nucleating agent on the surface of the laminated porous film.

Next, the components of the first layer will be described in detail.
<Description of polypropylene resin (A)>
The polypropylene resin used for the first layer is homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene. Alternatively, a random copolymer or block copolymer with an α-olefin such as 1-decene may be mentioned. Among these, homopolypropylene is more preferably used from the viewpoint of the mechanical strength of the laminated porous film.

Moreover, as a polypropylene resin, it is preferable that the isotactic pentad fraction (mmmm fraction) which shows stereoregularity is 80 to 99%. More preferably 83-98%, still more preferably 85-97%. If the isotactic pentad fraction is too low, the mechanical strength of the film may be reduced. On the other hand, the upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at the present time, but this is not the case when a more regular resin is developed in the industrial level in the future. is not.
The isotactic pentad fraction (mmmm fraction) is the same direction for all five methyl groups that are side chains with respect to the main chain of carbon-carbon bonds composed of arbitrary five consecutive propylene units. Means the three-dimensional structure located at or its proportion. Signal assignment of the methyl group region is as follows. It conforms to Zambelli et al (Macromolecules 8,687, (1975)).

  Moreover, it is preferable that Mw / Mn which is a parameter which shows molecular weight distribution of a polypropylene resin (A) is 2.0-10.0. More preferably, 2.0 to 8.0, and still more preferably 2.0 to 6.0 is used. This means that the smaller the Mw / Mn is, the narrower the molecular weight distribution is. However, when the Mw / Mn is less than 2.0, problems such as a decrease in extrusion moldability occur, and it is difficult to produce industrially. . On the other hand, when Mw / Mn exceeds 10.0, low molecular weight components increase, and the mechanical strength of the laminated porous film tends to decrease. Mw / Mn is obtained by GPC (gel permeation chromatography) method.

  Further, the melt flow rate (MFR) of the polypropylene-based resin is not particularly limited, but usually the MFR is preferably 0.5 to 15 g / 10 minutes, and 1.0 to 10 g / 10 minutes. It is more preferable. When the MFR is less than 0.5 g / 10 min, the resin has a high melt viscosity at the time of molding and the productivity is lowered. On the other hand, if it exceeds 15 g / 10 minutes, the mechanical strength of the film is insufficient, and problems are likely to occur in practice. MFR is measured according to JIS K7210 under conditions of a temperature of 230 ° C. and a load of 2.16 kg.

<Description of β crystal nucleating agent>
Examples of the β crystal nucleating agent used in the present invention include those shown below, but are not particularly limited as long as they increase the formation and growth of β crystals of polypropylene resin, and two or more types are mixed. May be used.
Examples of the β crystal nucleating agent include amide compounds; tetraoxaspiro compounds; quinacridones; iron oxides having a nanoscale size; potassium 1,2-hydroxystearate, magnesium benzoate or magnesium succinate, magnesium phthalate, etc. Alkali or alkaline earth metal salts of carboxylic acids represented by: aromatic sulfonic acid compounds represented by sodium benzenesulfonate or sodium naphthalenesulfonate; di- or triesters of dibasic or tribasic carboxylic acids; phthalocyanine blue Phthalocyanine pigments typified by: a two-component compound comprising component A which is an organic dibasic acid and a component B which is an oxide, hydroxide or salt of a Group IIA metal of the periodic table; a cyclic phosphorus compound; Made of magnesium compound And the like formed product, but shows a particularly preferred among them below.

Preferred β crystal nucleating agents include those represented by general formula (I);
R _Ib —NHCO—R _Ia —CONH—R _Ic (I)
General formula (II);
R _IIb -CONH-R _IIa -CONH-R _IIc (II)
Or general formula (III);
_{R IIIb -CONH-R IIIa -NHCO-} R IIIc (III)
(In each formula, R _Ia , R _IIa and R _IIIa are the same or different and each represents a divalent hydrocarbon group having 1 to 28 carbon atoms which may be substituted;
R _Ib , R _Ic , R _IIb , R _IIc , R _IIIb and R _IIIc are the same or different and each represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. )
An amide compound represented by

下記式（ｂ）；

下記式（ｃ）；

または、下記式（ｄ）；

で示される基を表す。化学式１〜４において、Ｒ_４およびＲ_５は同一または異なって水素原子、炭素数１〜１２の直鎖状または分岐鎖状のアルキル基、Ｒ_６およびＲ_７は同一または異なって炭素数１〜１２の直鎖状または分岐状のアルキレン基を表す。）
で示される化合物である。 Among them, as the amide compound represented by the general formula (I), (II), or (III), an amide compound represented by the following general formula (1), (2), or (3) is particularly preferable. It is mentioned as one mode of an agent.
The amide compound represented by the general formula (1) included in the general formula (I) is:
R ₂ —NHCO—R ₁ —CONH—R ₃ (1)
(In the formula, R ₁ represents a saturated or unsaturated aliphatic, alicyclic or aromatic dicarboxylic acid residue having ₁ to 28 carbon atoms;
R ₂ and R ₃ may be the same or different, and a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group,
The following formula (a);

Following formula (b);

Following formula (c);

Or the following formula (d);

Represents a group represented by In Chemical Formulas 1-4, R ₄ and R ₅ are the same or different and are a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and R ₆ and R ₇ are the same or different and have 1 to 1 carbon atoms. 12 linear or branched alkylene groups are represented. )
It is a compound shown by these.

下記式（ｆ）；

下記式（ｇ）；

または、下記式（ｈ）；

で示される基を表す。化学式５〜８において、Ｒ_１１は水素原子、炭素数１〜１２の直鎖状もしくは分岐鎖状のアルキル基、アルケニル基、シクロアルキル基またはフェニル基を表し、Ｒ_１２は炭素数１〜１２の直鎖状もしくは分岐状のアルキル基、シクロアルキル基またはフェニル基を表す。Ｒ_１３およびＲ_１４は同一または異なって、炭素数１〜４の直鎖状または分岐鎖状のアルキレン基を表す。）
で示される化合物である。
なお、Ｒ_８で示される「アミノ酸残基」におけるアミノ酸としては、天然のアミノ酸に限らず非天然のアミノ酸であってもよく、Ｄ−体またはＬ−体のいずれでもよく、α−、β−、γ−、ε−型のいずれのものでもよい。 The amide compound represented by the general formula (2) contained in the general formula (II) is:
R ₈ -CONH-R ₉ -CONH-R ₁₀ (2)
(Wherein R ₈ represents a saturated or unsaturated aliphatic, alicyclic or aromatic amino acid residue having 1 to 28 carbon atoms,
R ₉ and R ₁₀ may be the same or different, and a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group,
Following formula (e);

The following formula (f);

Following formula (g);

Or the following formula (h);

Represents a group represented by In Chemical Formulas 5 to 8, R ₁₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkenyl group, a cycloalkyl group, or a phenyl group, and R ₁₂ has 1 to 12 carbon atoms. A linear or branched alkyl group, a cycloalkyl group or a phenyl group is represented. R ₁₃ and R ₁₄ are the same or different and each represents a linear or branched alkylene group having 1 to 4 carbon atoms. )
It is a compound shown by these.
The amino acid in the “amino acid residue” represented by R ₈ is not limited to a natural amino acid but may be a non-natural amino acid, either a D-form or an L-form, and α-, β- , Γ-, and ε-types may be used.

下記式（ｊ）；

下記式（ｋ）；

または、下記式（ｌ）；

で示される基を表す。化学式９〜１２において、Ｒ_１８は水素原子、炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基、アルケニル基を示し、Ｒ_１９は炭素数１〜１２の直鎖状もしくは分岐状のアルキル基、シクロアルキル基またはフェニル基を表し、Ｒ_２０およびＲ_２１は同一または異なって、炭素数１〜３の直鎖状若しくは分岐鎖状のアルキレン基を表す。）
で示される化合物である。 The amide compound represented by the general formula (3) contained in the general formula (III) is:
R ₁₅ —CONH—R ₁₆ —NHCO—R ₁₇ (3)
(In the formula, R ₁₅ represents an aliphatic diamine residue having 1 to 24 carbon atoms, an alicyclic diamine residue or an aromatic diamino acid residue;
R ₁₆ and R ₁₇ may be the same or different and each is a C 3-12 cycloalkenyl group, cycloalkyl group,
Following formula (i);

Following formula (j);

Following formula (k);

Or the following formula (l);

Represents a group represented by In Chemical Formulas 9 to 12, R ₁₈ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkenyl group, and R ₁₉ is a linear or branched group having 1 to 12 carbon atoms. Represents an alkyl group, a cycloalkyl group or a phenyl group, and R ₂₀ and R ₂₁ are the same or different and each represents a linear or branched alkylene group having 1 to 3 carbon atoms. )
It is a compound shown by these.

The amide compound represented by the general formula (1) can be prepared by amidating a dicarboxylic acid and a monoamine.
Examples of the dicarboxylic acid include malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalenedicarboxylic Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diph Acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2, 2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3′-sulfonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 3,3′-oxydi Benzoic acid, 4,4′-oxydibenzoic acid, 3,3′-carbonyldibenzoic acid, 4,4′-carbonyldibenzoic acid, 3,3′-thiodibenzoic acid, 4,4′-thiodibenzoic acid, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyl dibenzoic acid, 4,4'-terephthaloyl dibenzoic acid, dithiosalicylic acid and the like.

  Examples of the monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-propylcyclohexylamine, 2-isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-isopropylcyclohexylamine, 2-tert-butylcyclohexylamine, 4-n-butylcyclohexylamine, 4-isobutylcyclohexylamine, 4-sec- Butylcyclohexylamine, 4-tert-butylcyclohexylamine, 4-n-pentylcyclohexylamine, 4-isopepe Tilcyclohexylamine, 4-sec-pentylcyclohexylamine, 4-tert-pentylcyclohexylamine, 4-hexylcyclohexylamine, 4-heptylcyclohexylamine, 4-octylcyclohexylamine, 4-nonylcyclohexylamine, 4-decylcyclohexylamine, 4-undecylcyclohexylamine, 4-dodecylcyclohexylamine, 4-cyclohexylcyclohexylamine, 4-phenylcyclohexylamine, cycloheptylamine, cyclododecylamine, cyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, α-cyclohexyl Propylamine, β-cyclohexylpropylamine, γ-cyclohexylpropylamine, aniline o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-cumidine, m-cumidine, p-cumidine, o -Tert-butylaniline, pn-butylaniline, p-isobutylaniline, p-sec-butylaniline, p-tert-butylaniline, pn-amylaniline, p-isoamylaniline, p-sec-amylaniline P-tert-amylaniline, p-hexylaniline, p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline, p-undecylaniline, p-dodecylaniline, p-cyclohexylaniline, o -Aminodiphenyl, m-aminodiphenyl, p Diaminodiphenyl, p- aminostyrene, benzylamine, alpha-phenylethylamine, beta-phenylethylamine, alpha-phenylpropylamine, beta-phenylpropylamine, .gamma.-phenylpropyl amine.

The amide compound represented by the general formula (2) can be prepared by amidating an amino acid with a monocarboxylic acid and a monoamine.
Examples of the amino acid include aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutanoic acid, β-aminobutanoic acid, γ-aminobutanoic acid, and α-amino-α-methylbutane. Acid, γ-amino-α-methylenebutanoic acid, α-aminoisobutanoic acid, β-aminoisobutanoic acid, α-amino-n-pentanoic acid, δ-amino-n-pentanoic acid, β-aminocrotonic acid, α- Amino-β-methylpentanoic acid, α-aminoisopentanoic acid, 2-amino-4-pentenoic acid, α-amino-n-caproic acid, 6-aminocaproic acid, α-aminoisocaproic acid, 7-aminoheptanoic acid, α-amino-n-caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 1- Minocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid, α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-aminocinnamic acid, 2-amino-4-phenylbutanoic acid, 4-amino- 3-phenylbutanoic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid 2-amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino No-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4- Amino-3-methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, 4- (4-aminophenyl) butanoic acid, 4 -Aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid, p-aminocinnamic acid, p-aminohippuric acid, 2-amino-1-naphthoic acid, 3-amino- 1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic acid, 6-amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-amino-1-naphthoic acid, 1 Amino-2-naphthoic acid, 3-amino-2-naphthoic acid, 4-amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid Acid, 8-amino-2-naphthoic acid and the like.

  Examples of the monocarboxylic acid include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, 3-methylcyclopentanecarboxylic acid, and 1-phenyl. Cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4- Butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-phenylcyclohexanecarboxylic acid, 1-phenylcyclohexa Carboxylic acid, cyclohexenecarboxylic acid, 4-butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-cycloheptenecarboxylic acid, 1-methylcycloheptanecarboxylic acid, 4-methylcycloheptanecarboxylic acid, cyclohexylacetic acid, benzoic acid, o -Methyl-benzoic acid, m-methyl-benzoic acid, p-methyl-benzoic acid, p-ethyl-benzoic acid, p-propyl-benzoic acid, p-butylbenzoic acid, p-tert-butylbenzoic acid, p- Examples include pentylbenzoic acid, p-hexylbenzoic acid, o-phenylbenzoic acid, p-phenylbenzoic acid, p-cyclohexylbenzoic acid, phenylacetic acid, phenylpropionic acid, and phenylbutanoic acid.

  As said monoamine, the thing similar to the monoamine which is a raw material of the amide type compound represented by General formula (1) is mentioned.

The amide compound represented by the general formula (3) can be prepared by amidating a diamine and a monocarboxylic acid.
Examples of the diamine include 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, , 2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1 , 4-bis (aminomethyl) cyclohexane, isophoronediamine, mensendiamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminodiph Nirusurufon, and the like.
As said monocarboxylic acid, the thing similar to the monocarboxylic acid which is a raw material of the amide type compound represented by General formula (2) is mentioned.

（式中のＲ_４１およびＲ_４２は同一でも異なっても良く、水素原子または炭素数１〜１８の置換されていてもよい炭化水素基、好ましくは水素原子、アルキル基、シクロアルキル基またはアリール基を表すか、或いはＲ_４１、Ｒ_４２および窒素原子が共同して含窒素複素環基を表し、好ましくはＲ_４１およびＲ_４２はそれぞれの端で相互に結合して共同して炭素数２〜６のアルキレン基を表す。）
で示されるテトラオキサスピロ化合物が挙げられる。 As another aspect of the particularly preferred β crystal nucleating agent, the following general formula (4):

(In the formula, R ₄₁ and R ₄₂ may be the same or different, and may be a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₄₁ , R ₄₂ and a nitrogen atom jointly represent a nitrogen-containing heterocyclic group, and preferably R ₄₁ and R ₄₂ are bonded to each other at each end to jointly have 2 to 6 carbon atoms. Represents an alkylene group of
The tetraoxaspiro compound shown by these is mentioned.

  Specific examples of the tetraoxaspiro compound include 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9- Bis {4- [N- (4-t-butylcyclohexyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- ( 2,4-di-t-butylcyclohexyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- (1-adamantyl) Carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N-phenylcarbamoyl) phenyl] -2,4,8,10-tetra Oxaspiro [5.5] undecane, 3,9-bis {4- [N- (4-t-butylphenyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- (2,4-di-t-butylphenyl) carbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9- Bis {4- [N- (1-naphthyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butylcarbamoyl) ) Phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-hexylcarbamoyl) phenyl] -2,4,8,10-tetra Oxaspiro [5.5] Unde 3,9-bis [4- (Nn-dodecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N- n-octadecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis (4-carbamoylphenyl) -2,4,8,10-tetraoxaspiro [ 5.5] undecane, 3,9-bis [4- (N, N-dicyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4 -(N, N-diphenylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butyl-N-cyclohexylcarbamoyl) Phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butyl-N-phenylcarbamoyl) phenyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (1-pyrrolidinylcarbonyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3 , 9-bis [4- (1-piperidinylcarbonyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like can be suitably used.

  Other particularly preferred β crystal nucleating agents include quinacridone type compounds such as quinacridone, dimethylquinacridone and dimethoxyquinacridone; for example, quinacridonequinone, 5,12-dihydro (2,3b) acridine-7-1,4- Mixed crystals of dione and quino (2,3b) acridine-6,7,13-1,4- (5H, 12H) -tetron, and quinacridonequinone type compounds such as dimethoxyquinacridonequinone: for example, dihydroquinacridone, dimethoxyhydroquinacridone and And dihydroquinacridone type compounds such as dibenzodihydroquinacridone.

（式中、ｎは１〜１２の自然数であり、
Ｒ_５１は水素原子、カルボキシル基、炭素数１〜１２の置換されていてもよい炭化水素基、好ましくは水素原子、カルボキシル基、炭素数１〜１２の直鎖状もしくは分岐鎖状のアルキル基、炭素数５〜８のシクロアルキル基または炭素数６〜１２のアリール基を表し、
Ｘは炭素数１〜１２の置換されていてもよい二価の炭化水素基、好ましくは置換されていてもよい炭素数６〜１２の二価の芳香族炭化水素基、より好ましくは炭素数１〜１２のアルキル基、炭素数５〜８のシクロアルキル基または炭素数６〜１２のアリール基で置換されていてもよい炭素数６〜１２の二価の芳香族炭化水素基を表す。）
で示されるイミド酸との塩が特に好ましい。
当該塩としては、例えば、フタロイルグリシン、ヘキサヒドロフタロイルグリシン、Ｎ−ナフタロイルアラニンまたはＮ−４−メチルフタロイルグリシンのカルシウム塩が例示できる。 Other particularly preferred β crystal nucleating agents include, for example, dicarboxylic acid salts of metals from group IIa of the periodic table, such as calcium salts of pimelic acid and calcium salt of suberic acid, and dicarboxylic acids and IIa of the periodic table Mention may be made of mixtures of metal salts from the group.
Among them, the metal from group IIa of the periodic table and the formula (5);

(In the formula, n is a natural number of 1 to 12,
R ₅₁ represents a hydrogen atom, a carboxyl group, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms,
X is an optionally substituted divalent hydrocarbon group having 1 to 12 carbon atoms, preferably an optionally substituted divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably 1 carbon atom. Represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with an alkyl group having -12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms. )
A salt with imide acid represented by is particularly preferred.
Examples of such salts include calcium salts of phthaloyl glycine, hexahydrophthaloyl glycine, N-naphthaloylalanine or N-4-methylphthaloyl glycine.

  As other aspects of the β crystal nucleating agent that is particularly preferred, the cyclic phosphorus compound represented by the general formula (6), fatty acid magnesium, aliphatic magnesium phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, general formula (7) A composition comprising at least one magnesium compound selected from the group consisting of a magnesium salt of a cyclic phosphorus compound represented by formula (8) and a magnesium phosphinate compound represented by formula (8), or a formula (9) And a composition comprising the cyclic phosphorus compound shown and at least one magnesium compound selected from the group consisting of a magnesium phosphinate compound represented by the general formula (8), magnesium sulfate and talc.

（式中、Ａｒ_１およびＡｒ_２は同一または異なって、置換されていてもよい炭素数６〜１２の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数１〜１８の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。）
で示される化合物である。 The cyclic phosphorus compound represented by the general formula (6) is

(In the formula, Ar ₁ and Ar ₂ are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
It is a compound shown by these.

（式中、Ａｒ_３およびＡｒ_４は同一または異なって、置換されていてもよい炭素数６〜１２の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数１〜１８の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。） The magnesium salt of the cyclic phosphorus compound represented by the general formula (7) is

(In the formula, Ar ₃ and Ar ₄ are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.

（式中、Ａｒ_５およびＡｒ_６は同一または異なって、置換されていてもよい炭素数６〜１２の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数１〜１８の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。）
で示される化合物である。 The magnesium phosphinate compound represented by the general formula (8) is:

(In the formula, Ar ₅ and Ar ₆ are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
It is a compound shown by these.

（式中、Ａｒ_７およびＡｒ_８は同一または異なって、置換されていてもよい炭素数６〜１２の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数１〜１８の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。）
で示される化合物である。 The cyclic phosphorus compound represented by the general formula (9) is

(In the formula, Ar ₇ and Ar ₈ are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
It is a compound shown by these.

Examples of the cyclic phosphorus compound represented by the general formula (6) include 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1-methyl-10-hydroxy-9. , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide 6-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 7-methyl-10-hydroxy-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, 8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 6,8-dimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,6,8-trimethyl- 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenance Len-10-oxide, 6-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-ethyl-10-hydroxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-diethyl-10-hydroxy-9,10 Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-triethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 2-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-i-propyl-10-hydroxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 8-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6, 8-di-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-o 2,6,8-tri-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-s-butyl-10-hydroxy- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 8-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1,8-di-s-butyl-10-hydroxy- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-s-butyl-10-hydroxy-9, 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 6-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-butyl-10-hydroxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 1,6-di-tert-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 2,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxy 2,7-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,8-di-t-butyl-10- Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 2,6,8-tri-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2- t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-amyl-10-hydroxy-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide 6,8-di-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-t-amyl-10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphafe Nanthrene-10-oxide, 6-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 Oxide, 8-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-octyl-10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospho Phenanthrene-10-oxide, 2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-10-hydroxy-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-cyclohexyl-10-hydroxy 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphafenance Len-10-oxide, 2,6,8-tri-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-phenyl-10-hydroxy- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 6-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-benzyl-10-hydroxy-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2- (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl) -10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8- (α-methylbenzyl)- 0-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 2,6-di (α, α-dimethylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6-t-butyl- 8-Methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-1 0-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa 10-phosphaphenanthrene-10-oxide, 6-benzyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6- (Α-methylbenzyl) -8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-cyclohexyl-10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-cycl Hexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2, 6-di-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-10- Examples include hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Yes.
These cyclic phosphorus compounds can be used alone, or two or more cyclic phosphorus compounds can be used in combination.

  Examples of the magnesium compound used in combination with the cyclic phosphorus compound represented by the general formula (6) as the β crystal nucleating agent used in the present invention include magnesium acetate, magnesium propionate, magnesium n-butyrate, magnesium i-butyrate, n- Magnesium valerate, magnesium i-valerate, magnesium n-hexanoate, magnesium n-octanoate, magnesium 2-ethylhexanoate, magnesium decanoate, magnesium laurate, magnesium myristate, magnesium myristate, magnesium palmitate, Magnesium palmitolate, magnesium stearate, magnesium oleate, magnesium linoleate, magnesium linolenate, magnesium arachidate, magnesium behenate, magnesium erucate, rig Magnesium serinate, magnesium serinate, magnesium montanate, magnesium melicinate, magnesium 12-hydroxyoctadecanoate, magnesium ricinoleate, magnesium cerebronate, magnesium (mono, dimixed) hexyl phosphate, (mono, dimixed) magnesium octyl phosphate, (Mono, dimixed) 2-ethylhexyl magnesium phosphate, (mono, dimixed) magnesium decyl phosphate, (mono, dimixed) magnesium lauryl phosphate, (mono, dimixed) magnesium myristyl phosphate, (mono, dimixed) magnesium palmitate (Mono, dimixed) magnesium stearyl phosphate, (mono, dimixed) magnesium oleyl phosphate, (mono, dimi Xdo) magnesium linoleate phosphate, (mono, dimixed) magnesium linoleyl phosphate, (mono, dimixed) magnesium docosyl phosphate, (mono, dimixed) magnesium erucyl phosphate, (mono, dimixed) magnesium tetracosyl phosphate, (mono, dimixed) Examples include magnesium hexacosyl phosphate, magnesium (mono, dimixed) octacosyl phosphate, magnesium oxide, magnesium hydroxide, and magnesium carbonate.

As the magnesium compound used in combination with the cyclic phosphorus compound represented by the above general formula (6) as the β crystal nucleating agent used in the present invention, the compound exemplified above as the cyclic phosphorus compound represented by the general formula (6) Magnesium salt, magnesium-bis (1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5-methyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (6-methyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-methyl-2,2′-biphenylene phosphinate), magnesium-bis ( 1′-hydroxy-5′-methyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy) -6'-methyl-2,2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-4 ', 6'-dimethyl-2,2'-biphenylene phosphinate), magnesium bis (5 , 4 ′, 6′-trimethyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5-ethyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium -Bis (1'-hydroxy-4'-ethyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-ethyl-2,2'-biphenylene phosphinate), magnesium -Bis (1'-hydroxy-4 ', 6'-diethyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-triethyl) 1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-i-propyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy -4′-i-propyl-2,2′-biphenylene phosphinate), magnesium bis (1′-hydroxy-6′-i-propyl-2,2′-biphenylene phosphinate), magnesium bis ( 1′-hydroxy-4 ′, 6′-di-i-propyl-2,2′-biphenylene phosphinate), magnesium-bis (5,4 ′, 6′-tri-i-propyl-1′-hydroxy -2,2'-biphenylene phosphinate), magnesium-bis (5-s-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium Bis (1′-hydroxy-4′-s-butyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-6′-s-butyl-2,2′-biphenylene phosphinate) ), Magnesium-bis (6,6′-di-s-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5,4 ′, 6′-tri-s-butyl) -1′-hydroxy-2,2′-biphenylene phosphinate), magnesium bis (5-tert-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium bis (1′- Hydroxy-4′-t-butyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-6′-t-butyl-2,2′-biphenylene phosphinate) Magnesium-bis (5,6′-di-t-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5,4′-di-t-butyl-1′-hydroxy -2,2'-biphenylene phosphinate), magnesium-bis (5,5'-di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (6,4 '-Di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4', 6'-di-t-butyl-2,2'- Biphenylene phosphinate), magnesium bis (5,4 ′, 6′-tri-t-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium bis (5-t-amyl-) 1'-hydro Xy-2,2′-biphenylene phosphinate), magnesium bis (1′-hydroxy-4′-t-amyl-2,2′-biphenylene phosphinate), magnesium bis (1′-hydroxy-6) '-T-amyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4', 6'-di-t-amyl-2,2'-biphenylene phosphinate), magnesium -Bis (5,4 ', 6'-tri-t-amyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-t-octyl-1'-hydroxy-2, 2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-4'-t-octyl-2,2'-biphenylene phosphinate), magnesium bis (1'-hydride) Xy-6'-t-octyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-t-octyl-2,2'-biphenylene phosphinate) ), Magnesium-bis (5,4 ′, 6′-tri-t-octyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5-cyclohexyl-1′-hydroxy-2) , 2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-cyclohexyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-6′-cyclohexyl-2). , 2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-cyclohexyl-2,2'-biphenylene phospho) Finate), magnesium-bis (5,4 ′, 6′-tri-cyclohexyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-phenyl-2) , 2′-biphenylene phosphinate), magnesium-bis (5-benzyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-benzyl-2, 2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-6'-benzyl-2,2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-4 ', 6'-di) -Benzyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-benzyl-1'-hydroxy-2, '-Biphenylene phosphinate), magnesium-bis [5- (α-methylbenzyl) -1'-hydroxy-2,2'-biphenylene phosphinate], magnesium-bis [1'-hydroxy-4'-( α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [1′-hydroxy-6 ′-(α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [1′-hydroxy-4 ′, 6′-di (α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [5,4 ′, 6′-tri (α-methylbenzyl) -1′-hydroxy-2,2′-biphenylene phosphinate], magnesium-bis [5,4′-di (α, α-dimethylbenzyl) -1′-hydroxy-2,2′- Phenylene phosphinate], magnesium-bis (1′-hydroxy-4′-t-butyl-6′-methyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-) Benzyl-6′-methyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-cyclohexyl-6′-t-butyl-2,2′-biphenylene phosphinate), Magnesium-bis (1′-hydroxy-4′-benzyl-6′-t-butyl-2,2′-biphenylene phosphinate), magnesium-bis [1′-hydroxy-4 ′-(α-methylbenzyl) −6′-t-butyl-2,2′-biphenylene phosphinate], magnesium-bis (1′-hydroxy-4′-t-butyl-6′-cyclohexyl-2, '-Biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-benzyl-6'-cyclohexyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-) t-butyl-6′-benzyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-cyclohexyl-6′-benzyl-2,2′-biphenylene phosphinate), Magnesium-bis (5,4′-di-t-butyl-6′-benzyl-1′-hydroxy-2,2′-biphenylene phosphinate) and magnesium-bis (5,4′-dicyclohexyl-6′-) Benzyl-1′-hydroxy-2,2′-biphenylene phosphinate) and the like.
These magnesium compounds can be used alone or in combination of two or more magnesium compounds.

  The mass ratio of the mixture of the cyclic phosphorus compound represented by the general formula (6) and the magnesium compound is not particularly limited, but is usually 0.01 to 100 parts by mass of the magnesium compound with respect to 1 part by mass of the cyclic phosphorus compound. The ratio is preferably 0.1 to 10 parts by mass.

Examples of the cyclic phosphorus compound represented by the general formula (9) as the β crystal nucleating agent used in the present invention include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1- Methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-methyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 7-methyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dimethyl-9,10-di Dro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-trimethyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2- Ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-ethyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 8-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-diethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 2,6,8-triethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-i-propyl-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 8-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-i-propyl-9,10-dihydro-9- Oxa-10-phosphenanthrene-10-oxide, 2,6,8-tri-i-propyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2- s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-s-butyl-9,10-dihydro-9-oxa-1 -Phosphaphenanthrene-10-oxide, 8-s-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 1,8-di-s-butyl-9 , 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-s-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, 8-t-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 1,6- -T-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-di-t-butyl-9,10-dihydro-9-oxa-10-phos Phaphenanthrene-10-oxide, 2,7-di-t-butyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,8-di-t-butyl -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2,6,8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-amyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-amyl -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-amyl-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2,6,8-tri-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-octyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- X-oxide, 8-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-octyl-9,10-dihydro-9-oxa 10-phosphenanthrene-10-oxide, 2,6,8-tri-t-octyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2-cyclohexyl- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 8- Cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-cyclohexyl-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 6-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-benzyl-9,10-dihydro-9-oxa-10-phosphenance Len-10-oxide, 6-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9,10-dihydro-9-oxa-10-phospho Phenanthrene-10-oxide, 6,8-di-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 2,6,8-tri-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- (α-methylbenzyl) -9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl) -9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 8 -(Α-Methylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di (α-methylbenzyl) -9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri (α-methylbenzyl) -9,10-dihydro-9-oxa-10-phosphafena Nsulene-10-oxide, 2,6-di (α, α-dimethylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8- Methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 6-cyclohexyl-8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-t-butyl-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl) -8-t-butyl-9,10-dihydro-9-o Sa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6-benzyl- 8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-benzyl-9,10-dihydro-9-oxa-10-phospho Phenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,6-di-t-butyl-8- Benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl And which may or may not be 8-benzyl-9,10-dihydro-9-oxa-10-phosphatonin phenanthrene-10-oxide.
These cyclic phosphorus compounds can be used alone, or two or more cyclic phosphorus compounds can be used in combination.

Examples of the magnesium compound used in combination with the cyclic phosphorus compound represented by the general formula (9) as the β crystal nucleating agent used in the present invention include the above-mentioned various magnesium phosphinate compounds, magnesium sulfate, and basic magnesium sulfate (magnesium). Examples thereof include oxysulfate) and talc. These magnesium compounds can be used alone or in combination of two or more magnesium compounds.
Although the mass ratio of the mixture of the cyclic phosphorus compound and the magnesium compound represented by the general formula (9) is not particularly limited, the magnesium compound is usually 0.01 to 100 parts by mass, preferably 0 with respect to 1 part by mass of the cyclic phosphorus compound. .1 to 10 parts by mass.

In the present specification, the “divalent hydrocarbon group” of the “optionally substituted divalent hydrocarbon group” includes a saturated linear divalent hydrocarbon group and an unsaturated linear group. Examples thereof include a divalent hydrocarbon group, a saturated cyclic divalent hydrocarbon group, and an unsaturated cyclic divalent hydrocarbon group.
Saturated linear divalent hydrocarbon groups include linear alkyl groups (eg, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl). C _1-10 alkyl group such as n-nonyl, etc.), and a group obtained by removing one terminal hydrogen atom, specifically, linear groups such as methylene, ethylene, propylene, butylene, pentylene, etc. And C _1-6 alkylene.
Examples of the unsaturated linear divalent hydrocarbon group include linear alkenyl groups (for example, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2- Pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl and other C _2-6 alkenyl groups, etc.) or a linear alkynyl group (eg ethynyl) 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4 - hexynyl, it includes C _2-6 1 or a group obtained by removing a hydrogen atom of the terminal alkynyl groups, etc.) and the like of 5-hexynyl and the like, in particular even Such as linear C _2-6 alkenylene or C _2-6 alkynylene and the like.

The saturated cyclic divalent hydrocarbon group may be any position such as a cycloalkyl group (eg, C _3-9 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, etc.) A group obtained by removing one hydrogen atom (preferably a carbon atom different from a carbon atom having a bond, more preferably a carbon atom at the most distant position) (for example, C _5-7 cycloalkylene). .
Examples of the unsaturated cyclic divalent hydrocarbon group include cycloalkenyl groups (for example, 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexene-1- Yl, C _3-6 cycloalkenyl groups such as 1-cyclobuten-1-yl, 1-cyclopenten-1-yl, etc.), cycloalkanedienyl groups (for example, 2,4-cyclopentanedien-1-yl, 2 , 4-cyclohexanedien-1-yl, C _4-6 cycloalkanedienyl groups such as 2,5-cyclohexanedien-1-yl), aryl groups (eg, C _6-12 aryl groups such as phenyl, naphthyl, etc.) A group in which one hydrogen atom at any position (preferably a carbon atom different from a carbon atom having a bond, more preferably a carbon atom at the most distant position) is removed (example: For example, C _6-12 arylene).

  Examples of the substituent of the “optionally substituted divalent hydrocarbon group” include a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.), a nitro group, a cyano group, and an optionally substituted group. Amino group, optionally substituted lower alkyl group, 1 to 5 halogen atoms (eg, fluorine, chlorine, bromine, iodine etc.) optionally substituted lower alkoxy group, esterified carboxyl Group, an optionally substituted carbamoyl group, and the like. These optional substituents may be substituted at 1 to 3 (preferably 1 to 2) at chemically acceptable positions.

In the present specification, examples of the hydrocarbon group of the “optionally substituted hydrocarbon group” include an aliphatic chain hydrocarbon group, an alicyclic hydrocarbon group, an aryl group, and an aralkyl group.
Examples of the “aliphatic chain hydrocarbon group” as an example of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups such as an alkyl group, an alkenyl group, and an alkynyl group.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylpropyl, n-hexyl, isohexyl, 1 , 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethylpropyl, 2-ethylbutyl, n-heptyl, 1-methylheptyl, 1-ethylhexyl, n-octyl, 1- _Examples thereof include C _1-10 alkyl groups (preferably C _1-6 alkyl etc.) such as methyl heptyl and nonyl.
Examples of the alkenyl group include vinyl, allyl, isopropenyl, 2-methylallyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 2 -Methyl-2-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl C _2-6 alkenyl groups such as 4-hexenyl and 5-hexenyl.
Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2- C _2-6 alkynyl groups such as hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like can be mentioned.

Examples of the “alicyclic hydrocarbon group” as an example of the hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups such as a cycloalkyl group, a cycloalkenyl group, and a cycloalkanedienyl group.
Examples of the “cycloalkyl group” include C _3-9 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and the like.
Examples of the “cycloalkenyl group” include 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 1-cyclobuten-1-yl, 1 -C _3-6 cycloalkenyl groups such as -cyclopenten-1-yl and the like.
Examples of the “cycloalkanedienyl group” include C _4-6 such as 2,4-cyclopentanedien-1-yl, 2,4-cyclohexanedien-1-yl, 2,5-cyclohexanedien-1-yl and the like. And cycloalkanedienyl group.

Examples of the “aryl group” as an example of the hydrocarbon group include a monocyclic or condensed polycyclic aromatic hydrocarbon group, specifically, C _6- such as phenyl, naphthyl, anthryl, phenanthryl, acenaphthylenyl and the like. _{And 14} aryl group.
Examples of the “aralkyl group” as an example of the hydrocarbon group include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, Examples thereof include C _7-19 aralkyl groups such as 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, 4-biphenylylmethyl, and the like.

  Examples of the substituent of the “optionally substituted hydrocarbon group” include an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and optionally substituted. A good aryl group, an optionally substituted cycloalkyl or cycloalkenyl group, an optionally substituted heterocyclic group, an optionally substituted amino group, an optionally substituted imidoyl group, a substituted An amidino group, an optionally substituted hydroxyl group, an optionally substituted thiol group, an optionally esterified carboxyl group, an optionally substituted carbamoyl group, an optionally substituted thiocarbamoyl group Halogen atoms (eg fluorine, chlorine, bromine, iodine, etc., preferably chlorine, bromine, etc.), cyano groups, nitro groups, sulfonic acid Acyl group, and the like acyl group derived from a carboxylic acid. These optional substituents may be substituted at 1 to 3 (preferably 1 to 2) at chemically acceptable positions.

  Specific examples of these particularly preferable β crystal nucleating agents include β crystal nucleating agent “NJESTER NU-100” manufactured by Shin Nippon Rika Co., Ltd., and specific examples of polypropylene resins to which β crystal nucleating agents are added include polypropylene manufactured by Aristech. “Bepol B-022SP”, polypropylene manufactured by Borealis “Beta (β) -PP BE60-7032”, polypropylene manufactured by mayzo “BNX BETAPP-LN”, and the like.

<Description of other components>
The first layer may contain additives or other components that are generally blended into the resin composition within a range that does not impair the object of the present invention and the characteristics of the first layer as described above. Examples of the additive include recycling resin, silica, talc, kaolin, carbonic acid, etc., which are added for the purpose of improving / adjusting the processability, productivity, and various physical properties of the laminated porous film. Inorganic particles such as calcium, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents And additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents. Specifically, the interfaces as antioxidants described in P154 to P158 of PLASTICS compounding agents, UV absorbers described in P178 to P182, and antistatic agents described in P271 to P275 Activators, lubricants described in P283-294, and the like.

[Explanation of the second layer]
Next, the second layer will be described.
The second layer is a porous layer made of a composition having a peak value of the crystal melting temperature higher than the peak value of the crystal melting temperature of the composition of the first layer.
As long as the second layer is composed of a composition having a large number of fine pores communicating in the thickness direction and having a peak value of the crystal melting temperature higher than that of the composition of the first layer as described above, any material can be used. You may have a structure. For example, it may have a structure in which fine pores are provided in a film-like material made of a thermoplastic resin composition, or a particulate or fibrous fine material aggregates to form a layer, and a gap between the fine materials. May be a structure in which the micropores are formed. The second layer of the present invention preferably has the former structure in which uniform fine pores can be formed and the porosity and the like can be easily controlled.

The thermal characteristics of the thermoplastic resin contained in the composition of the second layer are important. That is, it is necessary to select the thermoplastic resin so that the peak value of the crystal melting temperature of the composition constituting the second layer is higher than the peak value of the crystal melting temperature of the composition constituting the first layer. Specifically, the second layer preferably contains a thermoplastic resin (B) having a peak value of crystal melting temperature of 200 ° C. or higher, whereby the second layer has a breakdown temperature of 200 ° C. or higher for breaking the film, That is, it is preferable to use a heat-resistant layer that does not break below 200 ° C. The upper limit of the peak value of the crystal melting temperature is not particularly limited, but is preferably 400 ° C. or lower.
The peak value of the crystal melting temperature is a peak value of the crystal melting temperature collected at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter in accordance with JIS K7121.

<Description of thermoplastic resin (B) having a peak value of crystal melting temperature of 200 ° C. or higher>
The thermoplastic resin (B) having a crystal melting peak temperature of 200 ° C. or higher is not particularly limited as long as the crystal melting peak temperature is satisfied.
Specifically, for example, polyolefin resins such as Porimechirupente emissions, polyethylene terephthalate, polyester resins such as polybutylene terephthalate; Po polyphenylene ether, polyether ether ketone, polysulfone, polyether sulfone or polyphenylene sulfide Polyether resins such as 6 nylon, 6-6 nylon or 6-12 nylon; polystyrene resins; methacrylic resins; polyvinyl chloride resins; fluorine resins; heat-resistant thermoplastic resins such as aramid resins Is mentioned.
Among them, polyester resins, polystyrene resins, fluorine resins, olefin resins such as polymethylpentene, and the like can be preferably used. In particular, when considering use as a battery separator, from the viewpoint of chemical resistance and the like, polymethylpentene and fluorine-based resin are preferable as the thermoplastic resin.

Examples of the polyester resin include a copolymer of a dicarboxylic acid and a dialcohol component. More specifically, in addition to the above-mentioned polyethylene terephthalate, polybutylene terephthalate, polyarylate, polytrimethylene terephthalate or polyethylene naphthalate, etc. are mentioned, but from the viewpoint of improving the heat resistance of the laminated porous film of the present invention. Polybutylene terephthalate having a high crystallinity and a high crystallization rate is more preferably used.
The polyester resin can be produced by a known method, or a commercially available product may be used. For example, as the polybutylene terephthalate, a trade name “Duranex” (manufactured by Polyplastics Co., Ltd.) and a trade name “Novaduran” (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are available as commercial products.

As the polystyrene resin include a homopolymer of styrene. More specifically, atactic polystyrene, syndiotactic Indianapolis Chile down like.
Among these, syndiotactic polystyrene with high crystallinity is more preferably used from the viewpoint of improving the heat resistance of the laminated porous film of the present invention.
The polystyrene resin can be produced by a known method, or a commercially available product may be used. For example, as syndiotactic polystyrene, the trade name “Zarek” (manufactured by Idemitsu Kosan Co., Ltd.) is available as a commercial product.

Examples of the fluororesin include polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, and polyvinylidene fluoride. It is done. Among these, polyvinylidene fluoride is preferably used from the viewpoint of moldability.
The fluororesin can be produced by a known method, or a commercially available product may be used. For example, a trade name “Fluon” (manufactured by Asahi Glass Co., Ltd.) can be obtained as an ethylene-tetrafluoroethylene copolymer, and a trade name “Polyfluorone” (manufactured by Daikin Co., Ltd.) can be obtained as a commercial product as polytetrafluoroethylene.

Moreover, you may add the mixture of 2 or more types of resin in the 2nd layer in the range which does not impair the heat resistance characteristic of a laminated porous film, specifically, BD characteristic, as needed. In this case, mixing of the above-mentioned heat-resistant thermoplastic resins or mixing of the heat-resistant thermoplastic resin and another thermoplastic resin is preferable, and mixing of the heat-resistant thermoplastic resins is particularly preferable.
Other thermoplastic resins that can be mixed with the above heat-resistant thermoplastic resin include polyolefin resins such as low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene vinyl acetate copolymer, or polypropylene; Examples thereof include thermoplastic resins such as polyester resins such as polycarbonate. Among these, when considering use as a battery separator, it is preferable to use a polyolefin-based resin as another thermoplastic resin from the viewpoint of chemical resistance and the like.
Moreover, you may mix | blend a beta crystal nucleating agent with the said polypropylene resin in a 2nd layer.

Further, if necessary, the composition constituting the second layer includes a so-called rubber component such as a thermoplastic elastomer within a range that does not impair the heat resistance characteristics of the laminated porous film, specifically, the BD characteristics. It may be added. Examples of the thermoplastic elastomer include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.
In addition, the additive etc. which are generally mix | blended with a resin composition may be mix | blended with the 2nd layer in the range which does not impair the objective of the above-mentioned this invention and the characteristic of a 2nd layer. Specifically, it is the same as the illustration of the other component which can be mix | blended with the said 1st layer.

The second layer may contain a substance that promotes porosity. In particular, a filler is preferably added to the second layer. By inserting a filler, a porous structure can be obtained more efficiently and the shape of the pores can be easily controlled.
As the filler, any inorganic or organic filler can be used, and one or a combination of two or more can be used. Especially, it is preferable to use an inorganic filler from the viewpoint of heat resistance and the like.

  Examples of inorganic fillers include carbonates such as calcium carbonate, magnesium carbonate and barium carbonate; sulfates such as calcium sulfate, magnesium sulfate and barium sulfate; chlorides such as sodium chloride, calcium chloride and magnesium chloride; aluminum oxide, oxidation In addition to oxides such as calcium, magnesium oxide, zinc oxide, titanium oxide, and silica, silicates such as talc, clay, and mica can be used. Among these, barium sulfate is preferable from the viewpoint of chemical resistance.

  As the organic filler, resin particles having a crystal melting peak temperature higher than the crystal melting peak temperature of the thermoplastic resin contained in the second layer are preferable, and crosslinked resin particles having a gel fraction of about 4 to 10% are more preferable. . Examples of organic fillers include ultra high molecular weight polyethylene, polystyrene, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polytetrafluoroethylene, polyimide, polyether. Examples thereof include thermoplastic resins such as imide, melamine, and benzoguanamine, and thermosetting resins. Among these, cross-linked polystyrene and the like are particularly preferable.

  As an average particle diameter of a filler, it is 0.1-50 micrometers, for example, Preferably it is 0.3-10 micrometers, More preferably, it is 0.5-5 micrometers. When the average particle size is less than 0.1 μm, the dispersibility decreases due to aggregation of fillers, and it becomes difficult to uniformly disperse in the thermoplastic resin composition. Also, when the fine pores are formed by peeling the interface between the filler and the thermoplastic resin by stretching, the dispersibility of the filler decreases when the average particle size of the filler is less than 0.1 μm, When interfacial peeling is performed, the starting point of the porosity is insufficient, and it is difficult to efficiently obtain a laminated porous film. On the other hand, when the average particle diameter exceeds 50 μm, it is difficult to make the film thin, and the mechanical strength of the film is remarkably lowered.

  The amount of the filler blended is, for example, 50 to 400 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the second layer when the interface between the filler and the thermoplastic resin is peeled to form micropores. 50 to 300 parts by mass. When the amount of the filler is less than 50 parts by mass, the effect of blending such a filler that the desired good porous structure is hardly expressed cannot be obtained sufficiently. On the other hand, if the amount of filler exceeds 400 parts by mass, not only will it be liable to cause problems in the process such as resin burning at the time of molding, but also the stable moldability will be reduced.

A plasticizer may be added to the composition constituting the second layer. In particular, when a filler is blended in the composition, it is preferable to add a plasticizer for the purpose of improving the dispersibility of the filler.
Examples of the plasticizer include ester compounds, amide compounds, alcohol compounds, amine compounds, epoxy compounds, ether compounds, mineral oils, waxes, liquid silicones, fluorine oils, liquid polyethers, liquid polybutenes, liquid polybutadienes, and carboxylates. , Carboxylic acid compounds, sulfonates, sulfone compounds, amine salts, fluorine compounds, and the like.

  Specifically, plastic compounding agents [published by Taiseisha Co., Ltd., November 30, 1987, second edition issued] P31-P64, P83, P97-P100, P154-P158, P178-P182, P271-P275, P283-294 And the like. Further, the surfactant compounds listed in the new surfactant introduction [published by Sanyo Kasei Kogyo Co., Ltd., August 1992, third edition] can also be suitably used as the plasticizer.

More specifically,
Examples of the ester compound include tetraglycerin tristearate, glycerin tristearate, stearyl stearate, ethylene carbonate, distearyl carbonate, dioctyl naphthalate, and the like.
Examples of the amide compound include ethylene bis stearamide and hexamethylene bis stearamide.
Examples of the alcohol compound include stearyl alcohol, oleyl alcohol, dodecylphenol and the like.

Examples of the amine compound include dihydroxyethyl stearylamine and laurylamine.
Examples of amine salt compounds include stearyl dimethyl betaine and lauryl trimethyl ammonium chloride.
Examples of the epoxy compound include epoxy soybean oil.
Examples of the ether compound include triethylene glycol.
Mineral oil includes kerosene and naphthenic oil.
Examples of the wax include paraffin wax.
Examples of the carboxylate include calcium stearate and sodium oleate.
Examples of carboxylic acid compounds include stearic acid and caproic acid.
Examples of the sulfonate include sodium dodecylbenzenesulfonate.
Examples of the sulfone compound include sulfolane and dipropyl sulfone.

In view of the use of the laminated porous film of the present invention, the plasticizer is preferably a plasticizer having a melting point of 25 ° C. or higher and a boiling point of 140 ° C. or higher among those described above.
Here, the melting point of 25 ° C. or higher is defined as a crystal melting peak temperature of 25 ° C. or higher as measured by a differential scanning calorimeter, or a kinematic viscosity at 25 ° C. of 100,000 mm ² / sec or higher. To do.
The boiling point of 140 ° C. or higher means that the boiling point is clearly 140 ° C. or higher, or the mass after heating at 140 ° C. for 1 hour does not decrease by 10% or more with respect to the mass before heating.

  The blending amount of the plasticizer is 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin contained in the second layer. It is. When the blending amount of the plasticizer is less than 0.1 parts by mass, the effect of blending the plasticizer such that the desired good stretchability is hardly expressed and the non-uniform porous structure is likely to be sufficiently obtained. I can't get it. Moreover, when the compounding quantity of a plasticizer exceeds 30 mass parts, it will become easy to raise | generate the trouble on processes, such as resin burning and eye-gearing, in the case of film forming.

[Explanation of the third layer]
Next, the third layer will be described.
The third layer is a porous layer made of a composition having a peak value of crystal melting temperature lower than the peak value of crystal melting temperature of the composition of the first layer.
The third layer has many structures / structures as long as it has a large number of fine holes communicating in the thickness direction and the fine holes close at a lower temperature than the first layer as described above. Good. For example, it may have a structure in which the fine pores are provided in a film-like material made of a thermoplastic resin composition, or particulate or fibrous fine objects aggregate to form a layer, A structure in which the gap is the fine hole may be used. The third layer of the present invention preferably has the former structure in which uniform fine pores can be formed and the porosity and the like can be easily controlled.

The thermal characteristics of the thermoplastic resin contained in the thermoplastic resin composition constituting the third layer are also important. Specifically, it is preferable to include a thermoplastic resin (C) having a peak value of crystal melting temperature of 100 ° C. or higher and 150 ° C. or lower, whereby the third layer is closed at 100 ° C. or higher and 150 ° C. or lower. It is preferable that the shutdown layer has a function.
This crystal melting peak temperature is a peak value of the crystal melting temperature collected at a rate of temperature increase of 10 ° C./min using a differential scanning calorimeter in accordance with JIS K7121.

<Explanation of Thermoplastic Resin (C) whose Crystal Melting Temperature Peak Value is 100 ° C. or More and 150 ° C. or Less>
The thermoplastic resin (C) having a peak value of the crystal melting temperature of 100 ° C. or higher and 150 ° C. or lower is not particularly limited as long as the crystal melting peak temperature is satisfied. However, when considering use as a battery separator, from the viewpoint of chemical resistance, polyolefin such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene vinyl acetate copolymer, or polymethylpentene A series resin is preferable as the thermoplastic resin. In addition, polystyrene resin, polyacrylic resin, polyvinyl chloride, polyester resin, polyether resin, and polyamide resin that satisfy the peak value of the crystal melting temperature are also included.
In addition, as long as the said conditions are satisfy | filled, the other polypropylene resin different from the said polypropylene resin (A) can also be used.

Further, if necessary, in the third layer, a mixture of two or more kinds of resins may be used as the thermoplastic resin (C) within a range that does not impair the thermal characteristics of the laminated porous film, specifically, the SD characteristics. good. In this case, the above-mentioned mixing of polyolefin resins or the mixing of polyolefin resins and other thermoplastic resins is preferable, and the mixing of polyolefin resins is particularly preferable.
The thermoplastic resin (C) is particularly preferably a polyethylene resin such as low density polyethylene, high density polyethylene or linear low density polyethylene, or a mixture of a polyethylene resin and another polyolefin resin, and more preferably a polyethylene resin. Single is more preferred.

Density of the polyethylene resin is preferably 0.920~0.970g / cm ^3, more preferably 0.930~0.970g / cm ^3, 0.940~0.970g / cm ³ is more preferable. A density of 0.920 g / cm ³ or more is preferable because a first layer having an appropriate shutdown temperature can be formed. On the other hand, if it is 0.970 g / cm ³ or less, it is preferable in that a laminated porous film having a first layer having an appropriate shutdown temperature can be formed and that stretchability is maintained. The density can be measured according to JIS K7112 using a density gradient tube method.

Further, the melt flow rate (MFR) of the polyethylene resin is not particularly limited, but usually the MFR is preferably 0.5 to 15 g / 10 minutes, and 1.0 to 10 g / 10 minutes. It is more preferable. An MFR of 0.5 g / 10 min or more is preferable because the melt viscosity of the resin at the time of molding is sufficiently low, so that the productivity is excellent. On the other hand, if it is 15 g / 10 minutes or less, since it is close to the melt viscosity of the polypropylene resin to be mixed, dispersibility is improved, resulting in a homogeneous laminated porous film, which is preferable.
MFR is measured in accordance with JIS K7210 under conditions of a temperature of 190 ° C. and a load of 2.16 kg.

  In addition, the manufacturing method of resin (C) whose crystal melting peak temperature represented by polyethylene resin is 100 degreeC or more and 150 degrees C or less is not specifically limited, Well-known polymerization using the well-known olefin polymerization catalyst Examples of the method include a polymerization method using a multisite catalyst typified by a Ziegler-Natta type catalyst and a single site catalyst typified by a metallocene catalyst.

  Examples of other thermoplastic resins that can be mixed with the aforementioned polyolefin resins include styrene resins such as styrene, AS resin, ABS resin, or PMMA resin: polyvinyl chloride, fluorine resin, polyethylene terephthalate, polybutylene terephthalate. Ester resins such as polycarbonate or polyarylate; ether resins such as polyacetal, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone or polyphenylene sulfide; 6 nylon, 6-6 nylon, 6-12 nylon, etc. Examples thereof include thermoplastic resins such as polyamide-based resins.

In addition, if necessary, the thermoplastic resin composition constituting the third layer may be a so-called rubber component such as a thermoplastic elastomer as in the second layer described above, and the thermal characteristics of the laminated porous film. Specifically, it may be added as long as the SD characteristics are not impaired. As a thermoplastic elastomer, the thing similar to a 2nd layer can be used.
Furthermore, the additive etc. generally mix | blended with a resin composition may be mix | blended with the 3rd layer in the range which does not impair the objective of the above-mentioned this invention and the characteristic of a 3rd layer. Specifically, it is the same as that of the additive which can be mix | blended with a 1st layer and a 2nd layer.

The third layer may contain a substance that promotes porosity. In particular, a filler is preferably added to the third layer. By inserting a filler, a porous structure can be obtained more efficiently and the shape of the pores can be easily controlled.
As the filler, an inorganic or organic material similar to the filler in the second layer described above can be used, and these can be used alone or in combination of two or more. In view of heat resistance and the like, it is preferable to use an inorganic filler also in the third layer. The blending amount of the filler is the same as that of the second layer described above.

A plasticizer may be added to the composition constituting the third layer. In particular, when a filler is added to the composition, it is preferable to add a plasticizer for the purpose of improving the dispersibility of the filler.
As a plasticizer, the same thing as the above-mentioned 2nd layer can be used with the same compounding quantity.

[Description of laminated structure]
The laminated structure of the laminated porous film of the present invention will be described.
Most simple structure is a three-layer structure of the first layer and the second layer and the third layer. In the case of a three-layer configuration, each layer fulfills its function and does not affect other characteristics, so that any of the second layer / first layer / third layer, first layer / second layer / third layer is selected. The stacking order may be as follows. Next, a simple structure is in the form of three types and four layers. In this case, if it is necessary to give strength, the first layer can be increased between any layers or outside, and if more heat resistance is given, It is also possible to increase between or outside the layers. Similarly, the third layer can be increased to enhance the shutdown characteristics. Further, for example, a configuration of three types and five layers such as second layer / first layer / third layer / first layer / second layer may be adopted. Furthermore, the number of layers may be increased as necessary, such as 3 types, 6 layers, and 7 layers.

  Regarding the stacking ratio of the first layer, the second layer, and the third layer, the ratio of the first layer is 5 to 90%, the ratio of the second layer is 5 to 90%, and the ratio of the third layer in the total stacking thickness. Is preferably 5 to 90%. More preferably, the total thickness of the first layer is 10 to 80%, the second layer is 10 to 80%, and the third layer is 10 to 80%. Particularly preferably, the ratio of the first layer is 15 to 70%, the ratio of the second layer is 15 to 70%, and the ratio of the third layer is 15 to 70%. If even one of the three layers is less than 5%, the layer may not function sufficiently. Therefore, each layer is preferably 5% or more of the total laminated thickness.

[Description of shape and physical properties of laminated porous film]
The form of the film may be either flat or tube-like, but it is possible to take several pieces as a product in the width direction of the film-like material, so that the productivity is good, and the inner surface is treated with a coat or the like. From the viewpoint of being possible, etc., a planar shape is more preferable.
The thickness of the laminated porous film of the present invention is 1 to 500 μm, preferably 5 to 300 μm, and more preferably 7 to 100 μm. When using as a battery separator especially, 1-50 micrometers is preferable and 10-30 micrometers is more preferable. When used as a battery separator, if it is 1 μm or more, preferably 10 μm or more, substantially necessary electrical insulation can be obtained. For example, even when a large voltage is applied, short-circuiting is difficult and safety is excellent. Further, if the thickness is 50 μm or less, preferably 30 μm or less, the electric resistance of the laminated porous film can be reduced, so that the battery performance can be sufficiently secured.

The physical properties of the laminated porous film of the present invention can be freely adjusted by the composition of the first layer, the second layer, and the third layer, the number of laminations, the lamination ratio, combinations with layers having other properties, and the production method.
The laminated porous film of the present invention is characterized by having both SD characteristics and BD characteristics. That is, the SD characteristic is expressed at a temperature lower than the peak value of the crystal melting temperature of the polypropylene resin (A), while the BD temperature is expressed at a temperature higher than the peak value of the crystal melting temperature of the polypropylene resin (A). be able to.
In particular, the second layer includes a thermoplastic resin (B) having a peak value of crystal melting temperature of 200 ° C. or higher and is a heat-resistant layer that exhibits BD characteristics at 200 ° C. or higher, and the third layer has a crystal melting temperature of It is preferable that the shutdown layer includes the thermoplastic resin (C) having a peak value of 100 ° C. or higher and 150 ° C. or lower and exhibits SD characteristics at 100 ° C. or higher and 150 ° C. or lower. The SD characteristic and BD characteristic in this case will be described below.

(SD characteristics)
The laminated porous film exhibits SD characteristics at 100 ° C. or more and 150 ° C. or less. That is, the shutdown temperature of the laminated porous film of the present invention is 100 ° C. or higher and 150 ° C. or lower, preferably 110 ° C. to 145 ° C., more preferably 120 ° C. to 140 ° C.
For example, when a lithium ion battery incorporating the laminated porous film of the present invention as a battery separator is left in a car in summer, there is a possibility that the temperature may be close to 100 ° C. depending on the location. In such a case, if the shutdown temperature is 100 ° C. or more, it is preferable that the temperature is less than 100 ° C. because the micropores in the separator are retained and the lithium ion permeation function can be maintained as the separator. On the other hand, if the shutdown temperature is 150 ° C. or lower, for example, when the battery becomes abnormal and becomes a high temperature state of 100 ° C. or higher and 150 ° C. or lower, the micropores of the battery separator are immediately closed, and the lithium ions permeate. It is excellent in safety because it can be blocked and the subsequent temperature rise inside the battery can be prevented.

Here, the “shutdown temperature” refers to the lowest temperature at which the micropores are blocked. Specifically, when the laminated porous film of the present invention is heated by the method described in the examples, the air resistance after heating is low. The lowest temperature among the temperatures that are 10 times or more of the air resistance before heating.
As a means for adjusting the shutdown temperature to a desired temperature within the range of 100 ° C. or more and 150 ° C. or less, as the thermoplastic resin (C) contained in the third layer, the peak value of the crystal melting temperature close to the desired shutdown temperature is obtained. It can be carried out by selecting the thermoplastic resin (C) it has or by increasing or decreasing the layer ratio of the third layer.

(BD characteristics)
Furthermore, the laminated porous film is characterized by exhibiting BD characteristics at 200 ° C. or higher. That is, the breakdown temperature of the laminated porous film of the present invention is 200 ° C. or higher. If the breakdown temperature is 200 ° C. or higher, for example, when a battery using the laminated porous film of the present invention as a battery separator stores or heats up and the battery separator is exposed to a high temperature, the battery separator Since the film does not break and prevents direct contact between the positive electrode and the negative electrode, the battery is unlikely to explode or burn, making it extremely excellent in safety. More preferably, it is 220 degreeC or more, More preferably, it is 250 degreeC or more. The upper limit of the breakdown temperature is not particularly limited, but is about 400 ° C. due to the raw material processing temperature and the like.

Here, the “breakdown temperature” refers to the lowest temperature among the temperatures at which the laminated porous film of the present invention breaks when heated by the method described in the examples.
As a means for adjusting the breakdown temperature to a desired temperature in the range of 200 ° C. or higher, as the thermoplastic resin (B) contained in the second layer, heat having a peak value of the crystal melting temperature close to the desired breakdown temperature. This can be done by selecting the plastic resin (B), increasing or decreasing the layer ratio of the second layer, and the like.

The air-permeable resistance of the laminated porous film of the present invention is 1 to 10,000 seconds / 100 ml, preferably 5 to 3000 seconds / 100 ml, and more preferably 10 to 1000 seconds / 100 ml. If the air resistance is greater than 10,000 seconds / 100 ml, the numerical value of the air resistance is obtained in the measurement, but it means that the structure is quite poor in communication, so there may be substantially no communication. Many. On the other hand, if it is less than 1 second / 100 ml, the porous structure becomes rough and the pore diameter becomes too large, which is not preferable.
The air permeation resistance represents the difficulty of air passage in the film thickness direction, and is specifically expressed in the number of seconds required for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means poor communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction. If the air permeability resistance of the laminated porous film of the present invention is low, it can be used for various applications. For example, when used as a separator of a lithium ion secondary battery, a low air permeability resistance means that lithium ions can be easily transferred, which is preferable because the battery performance is excellent.
The air resistance is measured by the method described in the examples.

In the laminated porous film of the present invention, the porosity is preferably 5 to 80%, more preferably 20 to 70%. The porosity is an important factor for defining the porous structure. If the porosity is less than 5%, it is difficult to substantially obtain communication. Moreover, if the porosity is larger than 80%, handling becomes difficult from the viewpoint of the mechanical strength of the film, which is not preferable.
The porosity is measured by the method described in the examples.

In the laminated porous film of the present invention, the pin penetration strength is preferably 1.5 N or more, more preferably 2.0 N or more, and further preferably 3.0 N or more, regardless of the thickness.
Pin puncture strength greatly contributes to short-circuiting and productivity during battery production, particularly when the laminated porous film of the present invention is used as a battery separator. If the pin puncture strength is lower than 1.5N, the probability of occurrence of a short circuit due to film breakage due to foreign matter or the like during battery production is increased, which is not preferable.
On the other hand, the upper limit value of the pin puncture strength is not particularly specified, but usually 10N or less is used.
The pin puncture strength is measured by the method described in the examples.

Moreover, in the laminated porous film of this invention, it is preferable that the anisotropy is small from a viewpoint of film physical property. As an anisotropy index, it can be expressed by a ratio of tensile strength in the MD direction (take-off (flow) direction) and TD direction (perpendicular to MD) or a ratio of tear strength in the MD direction and TD direction.
For example, taking tensile strength as an example, the lower limit value of the “MD strength / TD strength ratio” is 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more as a ratio of the ratio. . If the “MD strength / TD strength ratio” is 0.05 or more, the physical properties are balanced, and in addition to handling, the porous structure finally has a smaller anisotropy film. Further, the upper limit value of the “MD strength / TD strength ratio” is 20 or less, preferably 10 or less, more preferably 7 or less. If the “MD strength / TD strength ratio” is 20 or less, the physical properties are balanced, and in addition to handling, the porous structure finally has a smaller anisotropy film.
The measuring method of the tensile strength is measured according to JIS K7127. Specifically, both MD and TD are measured at a width of 15 mm, a gap between chucks of 40 mm, and a crosshead speed of 200 mm / min.
The MD tensile strength is 50 MPa or more, preferably 100 MPa or more, more preferably 120 MPa or more. If it is 50 MPa or more, it is sufficient strength when handling the film. Although there is no particular upper limit, a range in which the balance with TD tensile strength does not deviate from the above range is preferable.
The TD tensile strength is 50 MPa or more, preferably 100 MPa or more, more preferably 120 MPa or more. If it is 50 MPa or more, it is sufficient strength when handling the film. Although there is no particular upper limit, a range in which the balance with the MD tensile strength does not deviate from the above range is preferable.

[Description of Method for Producing Laminated Porous Film]
Next, although the manufacturing method of the laminated porous film of this invention is demonstrated, this invention is not limited only to the laminated porous film manufactured by this manufacturing method.
The manufacturing method of the laminated porous film of this invention is divided roughly into the following two by the order of porous formation and lamination.
(A) From a composition having a crystalline melting peak temperature higher than the crystalline melting peak temperature of the composition of the porous film PP containing the polypropylene resin forming the first layer and the porous film PP forming the second layer. A porous film HR, and a porous film SD having a crystal melting peak temperature higher than the crystal melting peak temperature of the composition of the porous film PP forming the third layer, and at least porous Of laminating porous film PP, porous film HR and porous film SD.
(B) a layer (first layer) containing a polypropylene resin, a layer (second layer) made of a composition having a crystal melting peak temperature higher than the crystal melting peak temperature of the composition of the first layer, and the first layer A laminated nonporous film-like material comprising at least three layers of the composition (third layer) having a crystal melting peak temperature lower than the crystal melting peak temperature of the composition of How to make it porous.

Examples of the former method include a method of laminating the porous film PP, the porous film HR, and the porous film SD, and a method of laminating with an adhesive or the like.
The latter method includes a nonporous film PP containing a polypropylene resin and a nonporous film formed of a composition having a crystal melting peak temperature higher than the crystal melting peak temperature of the composition of the nonporous film PP. A nonporous film SD comprising a composition having a crystal melting peak temperature lower than the crystal melting peak temperature of the composition of the nonporous film PP and the nonporous film PP. There are a method in which the film-like material HR and the non-porous film-like material SD are laminated and then made porous, or a method in which the laminated non-porous film-like material is directly produced by coextrusion and then made porous.
In the present invention, a method using coextrusion is particularly preferred from the viewpoint of simplicity of the process and productivity.

The manufacturing method of the laminated porous film of the present invention can be classified by the method of making the second layer and the third layer separately from the above classification.
That is, since the first layer has β activity and / or β crystal generation power, it is possible to dissociate the interface between the β crystal and the amorphous by stretching to easily form micropores. On the other hand, as a method for making the second layer and the third layer porous, known methods such as a filler method, a phase separation method, an extraction method, a chemical treatment method, an irradiation etching method, a foaming method, or a combination of these techniques are used. Can be used .

The filler method is a method in which a non-porous layer or a non-porous film-like material is formed using a composition in which a filler is mixed with a resin, and the interface between the resin and the filler is peeled off to form micropores. is there.
The phase separation method is a technique called a conversion method or a microphase separation method, and forms micropores based on a phase separation phenomenon of a polymer solution. Specifically, it is roughly classified into (a) a method of forming micropores by phase separation of a polymer, and (b) a method of forming pores while forming micropores during polymerization. As the former method, there are a solvent gelation method using a solvent and a hot melt rapid solidification method, and either method may be used.

In the extraction method, an additive that can be removed in a subsequent step is mixed with the thermoplastic resin composition constituting the second layer and / or the third layer to form a non-porous layer or a non-porous film, and then the addition. It is a method of forming fine pores by extracting the agent with chemicals. Examples of the additive include a polymer additive, an organic additive, and an inorganic additive.
As an example using a polymer additive, a non-porous layer or a non-porous film-like material is formed using two types of polymers having different solubility in an organic solvent, and only one of the two types of polymers is used. A method of extracting the one polymer by dipping in a dissolving organic solvent can be mentioned. More specifically, a method of forming a nonporous layer or a nonporous film made of polyvinyl alcohol and polyvinyl acetate, and extracting polyvinyl acetate using acetone and n-hexane, or a block or graft copolymer And a method of forming a non-porous layer or a non-porous film-like material by containing a hydrophilic polymer and removing the hydrophilic polymer with water.

As an example using an organic material additive, a non-porous layer or a non-porous film-like material is formed by blending a substance soluble in an organic solvent in which the thermoplastic resin constituting the second layer and the third layer is insoluble. And a method of extracting and removing the substance by immersion in the organic solvent.
Examples of the substance include higher aliphatic alcohols such as stearyl alcohol or seryl alcohol, n-alkanes such as n-decane or n-dodecane, paraffin wax, liquid paraffin, or kerosene. These include isopropanol, ethanol, It can be extracted with an organic solvent such as hexane. In addition, water-soluble substances such as sucrose and sugar can also be mentioned as the substances, and these have the advantage of reducing the burden on the environment because they can be extracted with water.

The chemical treatment method is a method of forming micropores by chemically cleaving a part of a polymer substrate or conversely performing a binding reaction. More specifically, a method of forming micropores by chemical treatment such as redox agent treatment, alkali treatment, acid treatment, and the like can be mentioned.
The irradiation etching method is a method of forming minute holes by irradiating with neutron beam or laser.
The fusion method is a method of using a polymer fine powder such as polytetrafluoroethylene, polyethylene, or polypropylene and sintering the polymer fine powder after molding.
Examples of the foaming method include a mechanical foaming method, a physical foaming method, and a chemical foaming method, and any of them can be used in the present invention.

As a method for producing the laminated porous film of the present invention, for example, a thermoplastic resin composition comprising a polypropylene resin, a filler to the polypropylene crystalline melting temperature peak value is higher thermoplastic resin than the resin is blended A first layer and a second layer using a thermoplastic resin composition and a thermoplastic resin composition in which a filler is blended in a thermoplastic resin having a peak crystal melting temperature lower than that of the polypropylene resin. And a third non-porous film-like material comprising at least three layers, and stretching the multi-layer non-porous film material to form a large number of micropores having connectivity in the thickness direction. The manufacturing method of a laminated porous film is mentioned.

The production method of the laminated non-porous film is not particularly limited, and a known method may be used. For example, the thermoplastic resin composition is melted using an extruder, coextruded from a T die, and cooled and solidified with a cast roll. The method is mentioned. Moreover, the method of cutting open the film-like thing manufactured by the tubular method and making it planar is also applicable.
Regarding the stretching method of the laminated non-porous film-like material, there are methods such as a roll stretching method, a rolling method, a tenter stretching method, and a simultaneous biaxial stretching method, and these methods are used alone or in combination of two or more to perform uniaxial stretching or biaxial stretching. Do. Among these, biaxial stretching is preferable from the viewpoint of controlling the porous structure.

  Among these, as a more preferable production method, a thermoplastic resin composition containing a polypropylene-based resin having β activity and / or β crystal forming power that constitutes the first layer, and the above-mentioned that constitutes the second layer. A thermoplastic resin composition in which a filler is blended with a thermoplastic resin having a peak value of crystal melting temperature higher than that of the polypropylene resin, and a peak of crystal melting temperature than that of the polypropylene resin constituting the third layer A three-layered three-layer laminated non-porous film-like material is produced by T-die coextrusion so that a thermoplastic resin composition in which a filler is blended with a low-value thermoplastic resin is made porous by the filler method. And the manufacturing method of the lamination | stacking porous film which makes porous by carrying out biaxial stretching of the said lamination | stacking nonporous film-like material is demonstrated below.

The resin composition constituting the first layer, you at least the polypropylene resin (A) and β crystal nucleating agent. These raw materials are preferably mixed using a Henschel mixer, a super mixer, a tumbler type mixer or the like, or mixed by hand blending with all ingredients in a bag, and then preferably a single screw or twin screw extruder, a kneader, etc. Is pelletized after melt-kneading with a twin screw extruder.

  For the resin composition constituting the second layer, the raw materials such as the thermoplastic resin, filler, plasticizer and other additives as described in the explanation of the second layer are used, using a Henschel mixer, a super mixer, a tumbler mixer, etc. Are mixed and then melt-kneaded by a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized.

  For the resin composition constituting the third layer, raw materials such as the thermoplastic resin, filler, plasticizer and other additives as described in the explanation of the third layer are used, using a Henschel mixer, a super mixer, a tumbler mixer, etc. Are mixed and then melt-kneaded by a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized.

The pellets of the resin composition for the first layer, the pellets of the resin composition for the second layer, and the pellets of the resin composition for the third layer are separately fed into each extruder, and from the die for T-die co-extrusion Extrude. The type of the T die may be a multi-manifold type for type 3 and 3 layers, or a feed block type for type 3 and 3 layers.
The gap of the T die to be used is determined from the final required film thickness, stretching conditions, draft rate, various conditions, etc., but is generally about 0.1 to 3.0 mm, preferably 0.5. -1.0 mm. If it is less than 0.1 mm, it is not preferable from the viewpoint of production speed, and if it is larger than 3.0 mm, the draft rate is increased, which is not preferable from the viewpoint of production stability.

In extrusion molding, the extrusion processing temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 150 to 420 ° C, and more preferably 180 to 400 ° C. When the temperature is 150 ° C. or higher, the viscosity of the molten resin is preferably sufficiently low and excellent in moldability. On the other hand, at 420 ° C. or lower, the deterioration of the resin composition can be suppressed.
The cooling and solidifying temperature by the cast roll is very important in the present invention, and the β crystal of polypropylene resin can be generated and grown to adjust the ratio of β crystal in the film-like material. The cooling and solidification temperature of the cast roll is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, and still more preferably 100 to 130 ° C. By setting the cooling and solidification temperature to 80 ° C. or higher, the ratio of β crystals in the cooled and solidified film can be sufficiently increased, which is preferable. Further, it is preferable to set the temperature to 150 ° C. or lower because troubles such as the extruded molten resin sticking to and wrapping around the cast roll hardly occur and the film can be efficiently formed into a film.

By setting the cast roll in the temperature range, it is preferable to adjust the β crystal ratio of the polypropylene resin of the entire film-like product obtained before stretching to 30 to 100%. 40-100% is more preferable, 50-100% is still more preferable, and 60-100% is the most preferable. By setting the β crystal ratio in the entire film-like material before stretching to 30% or more, a film having good air permeability can be obtained because it is easily made porous by a subsequent stretching operation.
The β crystal ratio of the film-like material before stretching is detected when the film-like material is heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter. It is calculated by the following formula using the heat of crystal melting (ΔHmα) derived from the α crystal and the heat of crystal melting derived from the β crystal (ΔHmβ).
β crystal ratio (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100

  Next, the obtained laminated nonporous membrane is biaxially stretched. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of producing a laminated porous film excellent in SD characteristics and BD characteristics, which is the object 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. In addition, the extending | stretching to the take-up (flow) direction of a film-like thing is called "longitudinal stretching", and the extending | stretching to the perpendicular direction is called "lateral stretching."

  When sequential biaxial stretching is used, the stretching temperature needs to be appropriately selected depending on the composition of the resin composition to be used, the crystal melting peak temperature, the crystallinity, etc., but the stretching temperature in longitudinal stretching is generally 20 to 130 ° C., preferably Is controlled in the range of 40 to 120 ° C, more preferably 60 to 110 ° C. The longitudinal draw 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, it is possible to develop an appropriate pore starting point while suppressing breakage during stretching. On the other hand, the stretching temperature in transverse stretching is generally 100 to 160 ° C, preferably 110 to 150 ° C, and more preferably 120 to 145 ° C. The transverse draw ratio is preferably 2 to 10 times, more preferably 3 to 8 times, and further preferably 3 to 7 times. By transversely stretching within the above range, the pore starting point formed by longitudinal stretching can be appropriately expanded, and a fine porous structure can be expressed. The stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10,000% / min, and further preferably 2500 to 8000% / min.

  The laminated porous film thus obtained is preferably heat-treated at a temperature of about 100 to 170 ° C, preferably about 120 to 170 ° C for the purpose of improving dimensional stability. During the heat treatment step, a relaxation treatment of 1 to 15% may be performed as necessary. The laminated porous film of the present invention can be obtained by uniformly cooling and winding after the heat treatment.

  The laminated porous film of the present invention can be applied to various uses that require air permeability. Battery separators; Sanitary materials such as disposable paper diapers and sanitary items such as pads and bed sheets for absorbing body fluids; Medical materials such as surgical clothing or base materials for hot compresses; Materials for clothing such as jumpers, sportswear, and rainwear ; Building materials such as wallpaper, roof waterproofing material, heat insulating material, sound absorbing material; desiccant; moisture-proofing agent; oxygen scavenger; disposable body warmer; can be used very suitably as a material for packaging materials such as freshness preservation packaging or food packaging .

Especially, the lamination | stacking porous film of this invention is used suitably as a separator for nonaqueous electrolyte batteries, such as a lithium ion secondary battery utilized as power supplies, such as various electronic devices.
When used as the battery separator, the air permeability resistance is preferably 5 to 3000 seconds / 100 ml. More preferably, it is 20-2000 second / 100 ml, More preferably, it is 50-1000 second / 100 ml, Most preferably, it is 50-500 second / 100 ml.
If the air resistance is greater than 3000 seconds / 100 ml, the numerical value of the air resistance can be obtained in the measurement, but it means that the structure has very poor communication, so it can be practically used as a battery separator. In many cases, it is not a degree of air resistance. That is, it is preferable that the air permeation resistance is 3000 seconds / 100 ml or less because ion conductivity can be secured and sufficient battery characteristics can be obtained. On the other hand, if the air permeation resistance is 5 seconds / 100 ml or more, it is preferable because the pore diameter is appropriately small and the mechanical strength of the battery separator can be maintained.

In the laminated porous film of the present invention, other physical properties can be freely adjusted by the composition of the resin composition constituting the first layer to the third layer, the layer configuration, the production method, and the like.
For example, when used as a battery separator, the porosity is preferably 30 to 70%, more preferably 35 to 65%. If the porosity is 30% or more, ion permeability can be ensured and sufficient battery performance can be obtained. On the other hand, from the viewpoint of battery safety, the porosity is preferably 70% or less.

[Explanation of battery separator]
Next, a non-aqueous electrolyte battery containing the laminated porous film of the present invention as a battery separator will be described with reference to FIG.
Both electrodes of the positive electrode plate 21 and the negative electrode plate 22 are wound in a spiral shape so as to overlap each other via the battery separator 10, and the outside is stopped with a winding tape to form a wound body. When winding in this spiral shape, the battery separator 10 preferably has a thickness of 5 to 40 μm, particularly preferably 5 to 30 μm. When the thickness is 5 μm or more, the battery separator is not easily broken, and when the thickness is 40 μm or less, the battery area can be increased when wound in a predetermined battery can and the battery capacity can be increased. it can.

  A wound body in which the positive electrode plate 21, the battery separator 10 and the negative electrode plate 22 are integrally wound is housed in a bottomed cylindrical battery case and welded to the positive and negative electrode lead bodies 24 and 25. Next, the following electrolyte is injected into the battery can, and after the electrolyte has sufficiently penetrated into the battery separator 10 or the like, the positive electrode lid 27 is sealed around the opening periphery of the battery can via the gasket 26, and precharging and aging are performed. A cylindrical non-aqueous electrolyte battery is manufactured.

As the electrolytic solution, an electrolytic solution in which a lithium salt is used as an electrolytic solution and is dissolved in an organic solvent is used. The organic solvent is not particularly limited, but for example, propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, esters such as dimethyl carbonate, methyl propionate or butyl acetate, and nitriles such as acetonitrile. 1,2-dimethoxyethane, 1,2-dimethoxymethane, dimethoxypropane, 1,3-dioxolane, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran or 4-methyl-1,3-dioxolane, or sulfolane These may be used alone or in combination of two or more.
Among them, an electrolyte obtained by dissolving lithium hexafluorophosphate (LiPF ₆₎ at a rate of 1.4 mol / L in a solvent obtained by mixing 2 parts by mass of methyl ethyl carbonate relative to ethylene carbonate 1 part by weight is preferred.

As the negative electrode, an alkali metal or a compound containing an alkali metal integrated with a current collecting material such as a stainless steel net is used. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the compound containing an alkali metal include an alloy of an alkali metal and aluminum, lead, indium, potassium, cadmium, tin or magnesium, a compound of an alkali metal and a carbon material, a low potential alkali metal and a metal oxide, and the like. Or a compound with a sulfide or the like.
When a carbon material is used for the negative electrode, the carbon material may be any material that can be doped and dedoped with lithium ions, such as graphite, pyrolytic carbons, cokes, glassy carbons, a fired body of an organic polymer compound, Mesocarbon microbeads, carbon fibers, activated carbon and the like can be used.

  In this embodiment, as a negative electrode, a carbon material having an average particle size of 10 μm is mixed with a solution in which vinylidene fluoride is dissolved in N-methylpyrrolidone to form a slurry, and this negative electrode mixture slurry is passed through a 70-mesh net. After removing the large particles, uniformly apply to both sides of the negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm and dry, and then compression-molded with a roll press machine, cut, strip-shaped negative electrode plate and We use what we did.

  As the positive electrode, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, manganese dioxide, metal oxide such as vanadium pentoxide or chromium oxide, metal sulfide such as molybdenum disulfide, etc. are used as active materials. , These positive electrode active materials are combined with conductive additives and binders such as polytetrafluoroethylene as appropriate, and finished with a current collector material such as a stainless steel mesh as a core material. It is done.

In the present embodiment, a strip-like positive electrode plate produced as follows is used as the positive electrode. That is, lithium graphite oxide (LiCoO ₂ ) is added with phosphorous graphite as a conductive additive at a mass ratio of 90: 5 (lithium cobalt oxide: phosphorous graphite) and mixed, and this mixture and polyvinylidene fluoride are mixed with N -Mix with a solution dissolved in methylpyrrolidone to make a slurry. This positive electrode mixture slurry is passed through a 70-mesh net to remove large particles, and then uniformly applied to both sides of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, dried, and then compressed by a roll press. After forming, it is cut into a strip-like positive electrode plate.

[Description of Examples]
Next, although an Example and a comparative example are shown and it demonstrates in detail about the laminated porous film of this invention, this invention is not limited to these.
The take-up (flow) direction of the laminated porous film is referred to as a “longitudinal” direction, and the direction perpendicular thereto is referred to as a “lateral” direction.

(Examples and comparative examples)
The pellet for each layer was produced by the method shown to the following (a)-(c).
In addition, about the pellet (PP-1, (beta) PP-1, (beta) PP-2) of each polypropylene-type resin of the 1st layer, using the differential scanning calorimeter (DSC-7) by Parkin Elmer, 25 The temperature is raised from ℃ to 240 ℃ at a heating rate of 10 ℃ / min and held for 1 minute, then from 240 ℃ to 25 ℃, held at a cooling rate of 10 ℃ / min and held for 1 minute, and further heated from 25 ℃ to 240 ℃ Whether the crystal melting peak (Tmβ) derived from the β crystal is detected in the range of 145 ° C. or more and less than 160 ° C. when the temperature is re-heated at a rate of 10 ° C./min is also described.

(A) First layer [polypropylene resin]
-PP-1: A pellet of "Prime PP F300SV (trade name)" (MFR 3.0 g / 10 min) manufactured by Prime Polypro was used as it was.
At the time of reheating, only the crystal melting peak temperature (Tmα) derived from polypropylene α crystal was detected at 166 ° C., and the crystal melting peak temperature (Tmβ) derived from β crystal was not detected. That is, PP-1 alone did not have β activity.
・ ΒPP-1
After adding 0.1 part by mass of N, N′-dicyclohexyl-2,6-naphthalenedicarboxylic acid amide, which is a β crystal nucleating agent, to 100 parts by mass of the polypropylene resin (PP-1), hand blending is performed. Put into a twin screw extruder manufactured by Co., Ltd. (caliber 40 mmφ, L / D = 32), melt and mix at a set temperature of 280 ° C., cool and solidify the strand in a water bath, cut the strand with a pelletizer, and polypropylene A mixed pellet of resin (PP-1) and β crystal nucleating agent was prepared.
At the time of reheating, a crystal melting peak temperature (Tmβ) derived from polypropylene β crystal was detected at 154 ° C., and a crystal melting peak temperature (Tmα) derived from α crystal was detected at 168 ° C.
That is, βPP-1 has β activity, and the β activity calculated from the following formula was 80%.
β activity (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100
ΔHmβ: Crystal heat of fusion derived from β crystal detected in the range of 145 ° C. or higher and lower than 160 ° C. ΔHmα: Crystal heat of fusion derived from α crystal detected from 160 ° C. or higher and 175 ° C. or lower; βPP-2: β crystal nucleating agent Pellets of “Bepol B-022SP (trade name)” (MFR 0.3 g / 10 min) manufactured by Aristech, which is a blended polypropylene resin, were used.
At the time of reheating, the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene was detected at 151 ° C., and the crystal melting peak temperature (Tmα) derived from the α crystal was detected at 169 ° C.
That is, βPP-2 has β activity, and the β activity calculated from the above formula was 78%.

(B) Second layer As the thermoplastic resin, polymethylpentene “TPX RT-18” (HR-1) manufactured by Mitsui Chemicals, Inc. was used. HR-1 has an MFR of 26 g / 10 min and a Tm of 237 ° C.
As the filler, barium sulfate “B55” (FL-1) manufactured by Sakai Chemical Co., Ltd. was used. The average particle size of FL-1 is 0.66 μm.
As a plasticizer, Toyokuni Seiyaku "Hicaster Wax HCOP" (PL-1) was used.
Each raw material was blended at a ratio of HR-1 / FL-1 / PL-1 = 47.5 / 50 / 2.5, and a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (caliber 40 mmφ, L / D = 32) The melt was mixed at a set temperature of 260 ° C., and then the strand was cooled and solidified in a water tank, and the strand was cut with a pelletizer to produce a pellet. In Table 1, the pellet was designated as HR-CPD1.

(C) Third layer As a thermoplastic resin, polyethylene “Novatec HD HY530 (PE-1)” manufactured by Nippon Polyethylene Co., Ltd. was used. PE-1 has an MFR of 0.55 g / 10 min and a Tm of 134 ° C.
The filler and the plasticizer used were the same as those for the second layer.
Each raw material was blended at a ratio of PE-1 / FL-1 / PL-1 = 47.5 / 50 / 2.5, and a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (caliber 40 mmφ, L / D = 32) The mixture was melted and mixed at a set temperature of 220 ° C., and then the strand was cooled and solidified in a water tank, and the strand was cut with a pelletizer to produce a pellet. In Table 1, the pellet was designated as PE-CPD1.

  Next, the pellets prepared for each layer are put into a 40 mm single-screw extruder and extruded from a T-die through a three-kind three-layer or three-kind five-layer feed block in the examples and a two-kind two-layer feed block in the comparative example. The film was taken up with a cast roll having the temperature shown in Table 1 and cooled and solidified to obtain a film-like product having a width of 300 mm and a thickness of 180 μm. Next, using a film roll longitudinal stretching machine, the film was stretched in the longitudinal direction between the rolls at the stretching temperature and the stretching ratio listed in Table 1, and then stretched according to Table 1 in a film tenter facility manufactured by Kyoto Machine Co., Ltd. The film was stretched in the transverse direction at a temperature and a draw ratio. Furthermore, thermal relaxation was performed under the conditions described in Table 1 to obtain a laminated porous film.

  The obtained laminated porous film was measured and evaluated for various properties as follows, and the results are summarized in Table 2 below.

(1) Layer ratio A cross section of the laminated porous film was cut out and observed with a scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.), and the layer ratio was measured from the layer configuration and thickness.
(2) Thickness A thickness of 1/1000 mm was used to measure 30 in-plane thicknesses unspecified, and the average was taken as the thickness.
(3) Air permeability resistance (Gurley value)
The air resistance (second / 100 ml) was measured according to JIS P8117.
(4) Porosity The porosity is a numerical value indicating the proportion of the space portion in the film. The porosity was determined by measuring the substantial amount W1 of the film, calculating the mass W0 when the porosity was 0% from the density and thickness of the resin composition, and calculating from these values based on the following formula.
Porosity Pv (%) = {(W0−W1) / W0} × 100
(5) Pin puncture strength According to Japanese Agricultural Standards Notification No. 1019, the pin puncture strength was measured under the conditions of a pin diameter of 1.0 mm, a tip portion of 0.5R, and a pin puncture speed of 300 mm / min.

(6) SD characteristics The obtained film was cut into a 60 mm × 60 mm square, and as shown in FIG. 2 (A), an aluminum plate (material: JIS standard A5052, Size: 60 mm long, 60 mm wide, 1 mm thick) sandwiched between two sheets and restrained by a clip (made by KOKYO Corporation, double clip “Kuri-J35 (trade name)”) as shown in FIG. 2 (B) .
A film restrained by two aluminum plates is 99 ° C, 100 ° C, 101 ° C, 102 ° C, 103 ° C, ..., 148 ° C, 149 ° C, 150 ° C, etc. Place in oven (set by Tabai Espec, Tabi Gear Oven “GPH200 (product name)”, damper closed) at each temperature in increments of 1 ° C, and hold for 3 minutes after the oven internal temperature rises to each temperature Then, it was immediately taken out and cooled in an atmosphere at 25 ° C. for 30 minutes while being in a restrained state.
Then, the film was taken out from the aluminum plate, and the air permeation resistance of a circular portion of 40 mmΦ at the center was measured according to JIS P8117.
Of the temperatures at which the air resistance after the high-temperature heat treatment becomes 10 times or more of the air resistance before the heating, the lowest temperature is defined as the shutdown temperature. In addition, it is judged that those whose air permeability resistance is already 10 times or more before heating at 99 ° C. are less than 100 ° C., and those whose permeation resistance does not exceed 10 times before heating at 150 ° C. are over 150 ° C. did.
In the present invention, the shutdown temperature is preferably 100 ° C. or higher and 150 ° C. or lower, and thus evaluated as follows.
○: Shutdown temperature is 100 ° C. or higher and 150 ° C. or lower ×: Shutdown temperature is lower than 100 ° C. or higher than 150 ° C. If the film piece cannot be cut into a 60 mm × 60 mm square, a circular hole of 40 mmΦ is formed in the center. A sample may be prepared by adjusting the film so that it is placed.

(7) BD characteristics An oven (Tabai gear spec "GPH200" manufactured by Tabai Espec, Inc.) in which a film fixed to two aluminum plates in the same manner as FIGS. It was put in the damper closed state), taken out 2 minutes after the oven set temperature reached 200 ° C. again, and the state of the film was confirmed to determine the shape maintenance performance.
When the film was broken, it was evaluated as “X”, and when the shape was maintained, it was evaluated as “◯”.

(8) β activity Using a differential scanning calorimeter (DSC-7) manufactured by Perkin Elmer Co., Ltd., the temperature was raised from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min and held for 1 minute. Then, the temperature was lowered from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C./min and held for 1 minute, and further heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min. The presence or absence of β activity was evaluated as follows depending on whether or not a peak was detected at 145 ° C. to 160 ° C. which is the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene at the time of reheating.
○: When Tmβ is detected within the range of 145 ° C to 160 ° C (with β activity)
X: When Tmβ is not detected within the range of 145 ° C to 160 ° C (no β activity)
Note that the β activity was measured with a sample amount of 10 mg and the atmosphere gas as nitrogen.

(9) β-Crystal Forming Power As in the case of the measurement of the SD characteristic, the film was cut into a 60 mm long × 60 mm wide square and fixed as shown in FIGS. 2 (A) and 2 (B).
The film in a state of being restrained by two aluminum plates is placed in a ventilation constant temperature thermostat (model DKN602, manufactured by Yamato Kagaku Co., Ltd.) having a set temperature of 180 ° C. and a display temperature of 180 ° C., and held for 3 minutes. The temperature was changed and gradually cooled to 100 ° C. over 10 minutes. When the display temperature reaches 100 ° C., the film is taken out and cooled in an atmosphere of 25 ° C. for 5 minutes while being restrained by two aluminum plates. Wide-angle X-ray measurement was performed on a 40 mmφ circular portion.
-Wide-angle X-ray measuring device: manufactured by Mac Science Co., Ltd. Model No. XMP18A
X-ray source: CuKα ray, output: 40 kV, 200 mA
Scanning method: 2θ / θ scan, 2θ range: 5 ° to 25 °, scanning interval: 0.05 °, scanning speed: 5 ° / min
About the obtained diffraction profile, the presence or absence of the β crystal generation force was evaluated from the peak derived from the (300) plane of the β crystal of polypropylene as follows.
◯: When a peak is detected in the range of 2θ = 16.0 ° to 16.5 ° (with β crystal forming ability)
X: When a peak was not detected in the range of 2θ = 16.0 ° to 16.5 ° (no β crystal formation ability)
When the film piece cannot be cut into a 60 mm × 60 mm square, the sample may be prepared by adjusting so that the film is placed in a circular hole of 40 mmΦ in the center.

From Table 2, Comparative Example 1 consisting of two layers of a first layer and a third layer using a polypropylene resin not having β activity can be broken during stretching to produce a laminated porous film. There wasn't. Comparative Example 2 comprising the first layer and the third layer did not have the second layer to be the heat-resistant layer, but had SD characteristics, but did not have the BD characteristics at 200 ° C. In addition, Comparative Example 3 including the first layer and the second layer without the third layer had BD characteristics but did not have SD characteristics in the range of 100 ° C. to 150 ° C.
On the other hand, the laminated porous films of Examples 1 to 5 including the first layer to the third layer defined in the present invention have both the SD characteristic in the range of 100 ° C. to 150 ° C. and the BD characteristic at 200 ° C. It was excellent. Further, it has air resistance suitable as a battery separator, and also has an appropriate strength.

  The laminated porous film of the present invention can be suitably used as a battery separator because it has sufficient strength while maintaining strength and can exhibit excellent SD characteristics and BD characteristics.

It is a partially broken perspective view of the nonaqueous electrolyte battery which has stored the lamination porous film of the present invention as a battery separator. (A) (B) is a figure explaining the restraint method of the film in the measurement of SD characteristic in an Example, BD characteristic, and (beta) crystal formation power.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Battery separator 20 Nonaqueous electrolyte battery 21 Positive electrode plate 22 Negative electrode plate

Claims (15)

A laminated porous film comprising at least a first layer to a third porous layer,
The first layer is a layer made of a composition containing a β crystal nucleating agent in a polypropylene resin,
The second layer is a layer made of a composition having a peak value of crystal melting temperature higher than a peak value of crystal melting temperature of the composition of the first layer,
The third layer is a layer made of a composition having a peak value of crystal melting temperature lower than a peak value of crystal melting temperature of the composition of the first layer,
The first layer micropores by applying the extension Shin is formed, also the second and third layers filler method, phase separation method, an extraction method, a chemical treatment method, an irradiation etching method, is selected from foaming Micropores are formed by applying one or more methods , and
A laminated porous film having β activity and / or β crystal-forming ability.   The laminated porous film according to claim 1, which has a three-layer structure of second layer / first layer / third layer or first layer / second layer / third layer.   The laminated porous film according to claim 1, which has a laminated structure of four or more layers.   The polypropylene-based resin has an isotactic pentad fraction (mmmm fraction) of 80 to 99%, and Mw / Mn, which is a parameter indicating a molecular weight distribution, of 2.0 to 10.0. The laminated porous film according to claim 3.   The laminated porous film according to any one of claims 1 to 4, wherein the second layer and the third layer contain an inorganic filler at a ratio of 50 to 400 parts by mass with respect to 100 parts by mass of the resin. .   The laminated porosity according to any one of claims 1 to 5, wherein the β crystal nucleating agent is blended at a ratio of 0.0001 to 5.0 parts by mass with respect to 100 parts by mass of the polypropylene resin. the film.   The second layer according to any one of claims 1 to 6, wherein the second layer includes a thermoplastic resin having a peak value of crystal melting temperature of 200 ° C or higher, and is a heat-resistant layer having a breakdown temperature for breaking the film of 200 ° C or higher. The laminated porous film according to Item.   The thermoplastic resin having a crystal melting temperature peak value of 200 ° C. or higher in the second layer is at least one selected from the group consisting of polyester resins, polystyrene resins, fluorine resins, and polymethylpentene resins. The laminated porous film according to claim 7.   The third layer includes a thermoplastic resin having a peak value of a crystal melting temperature of not less than 100 ° C and not more than 150 ° C, and is a shutdown layer having a function of closing holes at not less than 100 ° C and not more than 150 ° C. The laminated porous film according to claim 8.   The laminated porous film according to claim 9, wherein the thermoplastic resin having a peak crystal melting temperature of the third layer of 100 ° C. or higher and 150 ° C. or lower is a polyethylene resin.   2. The thickness is 1 to 500 [mu] m, and the ratio of the first layer is 5 to 90%, the ratio of the second layer is 5 to 90%, and the ratio of the third layer is 5 to 90% of the total laminated thickness. The laminated porous film according to any one of claims 10 to 10.   The laminated porous film according to any one of claims 1 to 11, which has an air permeability resistance of 1 to 10,000 seconds / 100 ml.   The laminated porous film according to any one of claims 1 to 12, wherein the pin puncture strength is 1.5 N or more.   A battery separator comprising the laminated porous film according to any one of claims 1 to 13, and having an air permeability resistance of 5 to 3000 seconds / 100 ml.   A battery comprising the battery separator according to claim 14 incorporated therein.

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