JP5712236B2 - 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 good volumetric efficiency when mounted on devices, leading to miniaturization and weight reduction 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.

  In addition, separators with appropriate shutdown characteristics have recently been used. The shutdown characteristic is a function of closing the micropores of the battery separator when the temperature becomes high, and the lowest temperature among the temperatures at which the micropores are closed is called a shutdown temperature. The shutdown characteristic is an important characteristic that contributes to safety when a battery separator is incorporated in a lithium ion secondary battery. For example, when the battery becomes abnormal due to abnormalities and becomes a high temperature state, the battery separator having a shutdown characteristic closes the micropores and blocks ion conduction inside the battery, thereby preventing a subsequent temperature rise inside the battery. . In particular, with the recent increase in capacity of batteries, the need for this characteristic has further increased as the importance of battery safety has increased.

In response to such a request, Japanese Patent No. 3128132 (Patent Document 1) proposes a method of manufacturing a battery separator made of a mixed resin of polyethylene and polypropylene.
However, the production method of the present invention involves stretching the mixed resin in a uniaxial direction at a low temperature and further stretching in the same direction at a high temperature, and the resulting porous film is very easy to tear along the stretching direction. Have.
In addition, both the low-temperature stretching and the high-temperature stretching have a problem that the stretching speed is greatly limited and the productivity is very poor.

On the other hand, various methods for obtaining a porous film by stretching a polypropylene sheet containing β crystals have been proposed.
For example, Japanese Patent No. 2509030 (Patent Document 2) proposes a microporous film of superpermeable polypropylene obtained by biaxial stretching from an original polypropylene film having a high β crystal content (K> 0.5).
International Publication No. 2002/066233 pamphlet (Patent Document 3) proposes a polypropylene porous film obtained by sequentially biaxially stretching a polypropylene containing acicular β crystals and a method for producing the same.
The production methods described in the invention all use a biaxial stretching method, and the resulting porous film has isotropic mechanical strength and exhibits an excellent value. However, the porous film obtained by the present invention does not have a shutdown characteristic that greatly contributes to the safety of the battery, and in order to use these porous films as a battery separator, the safety of the battery is ensured. There was a problem.

In JP-A-9-255804 (Patent Document 4), a resin composition comprising polypropylene, polyethylene, and a β crystal type nucleating agent is used, and the crystal phase of the polypropylene component in the resin composition is substantially a β crystal phase. There is provided a method for producing a microporous membrane characterized by melt-molding into a certain film-like material and then stretching the film-like material at 60 to 135 ° C.
However, the invention does not describe a shutdown characteristic for ensuring the safety of the battery, and completely discusses a change in the thermal air permeability characteristic that is very important when used as a battery separator. Absent. Therefore, there is no description or even suggestion regarding the crystal melting peak temperature of polyethylene.

Japanese Patent No. 3128132 Japanese Patent No. 2509030 International Publication No. 2002/066233 Pamphlet Japanese Patent Laid-Open No. 9-255804

  An object of the present invention is to provide a laminated porous film having excellent air permeability characteristics and mechanical strength and having shutdown characteristics.

As a result of intensive studies on the problems of the prior art, the present inventors have succeeded in obtaining a laminated porous film that can solve the problems, and have completed the present invention. That is, a laminated porous film having at least two layers of a layer that exhibits shutdown characteristics and a layer that improves mechanical strength, and a polypropylene resin and a crystal melting peak temperature of 100 to 150 as a layer that exhibits shutdown characteristics. The problem of the present invention is solved by using a layer containing a thermoplastic resin at 0 ° C. and using a layer containing a large amount of polypropylene resin as a layer for improving mechanical strength. In addition, since the laminated porous film of the present invention has a β activity and / or β crystal generation ability as a whole or a layer containing a polypropylene resin having β activity, a fine porous layer is provided. And excellent air permeability characteristics can be exhibited.
In particular, when a film-like material molded from a resin composition containing β crystals is produced by successive biaxial stretching, even if no additives such as fillers are used, a large number of fine pores can be easily provided to make it porous. can do.

The laminated porous film of the present invention include the following two aspects.
As a first aspect, a laminated porous film in which at least two porous layers are laminated,
The two layers containing Mutotomoni a polypropylene resin having β activity, seen including a crystal thermoplastic resin melting peak temperature of 100 to 150 ° C., with different content of the thermoplastic resin of the second layer And a pinned strength is 1.5 N or more .
As a second aspect, a laminated porous film in which at least two porous layers are laminated,
The two layers viewed contains a thermoplastic resin containing Mutotomoni crystal melting peak temperature of 100 to 150 ° C. The polypropylene resin, the two layers are made different content of the thermoplastic resin,
and have a β activity and / or β crystal generation power, and a laminated porous film, wherein the pin stab strength is not less than 1.5 N.

The presence or absence of “β activity” in the laminated porous film of the present invention is determined to have β activity when a crystal melting peak temperature derived from β crystal is detected by a differential scanning calorimeter described later.
In addition, the presence or absence of “β crystal formation power” is determined to have β crystal formation power when a diffraction peak derived from β crystal is detected by measurement of β crystal generation power using an X-ray analyzer described later. Deciding.
The β activity and / or β crystal generation force is the state of the laminated porous film when the laminated porous film of the present invention is composed of only the two layers or when other porous layers are laminated. It is measured by.

  It is preferable that a β crystal nucleating agent is blended in the composition forming at least one of the two layers to have the β activity and / or the β crystal generation ability. Further, it is preferable that a β-crystal nucleating agent is blended in at least one of the two layers of polypropylene resin so as to have the β activity and / or the β crystal generation ability. The blending amount of the β crystal nucleating agent is preferably 0.0001 to 5.0 parts by mass with respect to 100 parts by mass of the polypropylene resin.

In any of the above embodiments, in at least one of the layers containing a polypropylene resin and a thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C., a mixing mass ratio of the polypropylene resin and the thermoplastic resin Is preferably polypropylene resin / thermoplastic resin = 10-90 / 90-10.
The thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C. is preferably a polyethylene resin.

In the laminated porous film of the present invention, the shutdown temperature at which the pores are closed is preferably more than 100 ° C and 160 ° C or less.
In the present invention, the “shutdown temperature” refers to the lowest temperature at which the micropores are blocked, specifically, the air resistance after heating when the laminated porous film of the present invention is heated by the method described in the examples. Is the lowest temperature among the temperatures at which the air permeation resistance before heating is 10 times or more.
Moreover, it is preferable that the air permeation resistance measured based on JISP8117 of a laminated porous film is 1-10000 second / 100 ml. Furthermore, according to Japanese Agricultural Standards Notification No. 1019, the pin puncture strength measured under the conditions of a pin diameter of 1.0 mm, a tip portion 0.5R, and a pin puncture speed of 300 mm / min is 1.5 N or more .
Moreover, when the air permeation resistance measured based on JIS P8117 of the laminated porous film of the present invention is 5 to 3000 seconds / 100 ml, it can be suitably used as a battery separator.
Furthermore, the present invention provides a battery incorporating this battery separator, and the battery can ensure higher safety than before.

According to the present invention, it is possible to provide a laminated porous film having excellent air permeability characteristics and mechanical strength and having shutdown characteristics, and the laminated porous film is particularly suitably used for a battery separator. can do.
More specifically, in the present invention, by Oite crystal melting peak temperature in the layer containing the polypropylene resin is further blended the thermoplastic resin is 100 to 150 ° C., without rupture of the film itself, The air permeability resistance of the film can be changed by closing the micropores of the film. This function greatly contributes to ensuring the safety of the battery as a shutdown characteristic when the laminated porous film of the present invention is used for a battery separator.
Furthermore, in the present invention, since the layer that improves the mechanical strength is laminated on the layer that exhibits the above-described shutdown characteristics, it has excellent mechanical strength. Therefore, when winding the electrode and separator in battery manufacturing, or when the electrode repeatedly expands and contracts during charge and discharge, the separator is broken due to electrode irregularities and burrs, causing a short circuit between the two electrodes. Hard to happen. And since the lamination | stacking porous film of this invention has (beta) activity and / or (beta) crystal formation power, it can provide a fine porous layer and can exhibit the outstanding air permeability characteristic.

The laminated porous film of the present invention does not require strict control of production conditions, and can be produced easily and efficiently.
In the present invention, it is made porous by stretching treatment. Since it is not necessary to remove the additive for making porous with a solvent, there is little adverse effect on the environment, and there is no deterioration of the separator characteristics due to the remaining of the additive. Furthermore, since a filler for making it porous is not included, a lighter porous film can be provided.
Further, in Patent Document 4, in the example, the biaxial stretching in the longitudinal direction and the transverse direction are stretched under the same temperature condition, but an ideal porous structure can be formed by further selecting the stretching treatment conditions, and as a result. A porous film having low air permeability resistance can be obtained.

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 a shutdown characteristic and (beta) crystal formation power.

Hereinafter, an embodiment of the laminated porous film of the present invention and an application form to a battery as a battery separator will be described in detail.
The laminated porous film of the present invention has a configuration in which at least two porous layers are laminated in any embodiment.

[ Reference embodiment]
In the laminated porous film of the reference embodiment, the two porous layers include a polypropylene resin (hereinafter referred to as “PP resin”), and one of the two layers has a crystal melting peak temperature of 100 to 150 ° C. A layer (PP-S layer) containing a thermoplastic resin (hereinafter referred to as “LM resin”), while the other layer does not contain a thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C. It is the product layer porous film according to (PP-N layer). And the laminated porous film of this invention has (beta) activity and / or (beta) crystal formation 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.

Presence or absence of the β activity is determined by performing differential thermal analysis of the laminated porous film using a differential scanning calorimeter and determining whether or not a crystal melting peak temperature derived from β crystals of the polypropylene resin is detected. doing.
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 laminated porous film preferably has a high β activity, 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. As a result, a separator for a lithium ion battery 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 is performed on a laminated porous film that has been subjected to heat treatment at 170 ° C. to 190 ° C., which is a temperature exceeding the melting point of polypropylene resin (PP resin), and slowly cooled to produce and grow β crystals. When a 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 β crystal forming power.
Details on 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 a method for obtaining the β activity and / or β crystal generation power of the porous layer described above, as described in a method in which a substance that promotes the formation of α crystal of a polypropylene resin is not added, or as described in Japanese Patent No. 3739481 The method of adding the polypropylene which performed the process which generates a peroxide radical, the method of adding a (beta) crystal nucleating agent to a composition, etc. are mentioned.
In particular, it is preferable that a β crystal nucleating agent is added to the composition forming at least one of the two layers to obtain β activity and / or β crystal generation 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 to obtain a laminated porous film having β activity and / or β crystal generation ability. it can.
In particular, it is preferable that a β crystal nucleating agent is blended in both of the two layers, and both the two layers have β activity and / or β crystal generation ability.

In the present invention, the β crystal nucleating agent is preferably blended with a polypropylene resin. The ratio of the β-crystal nucleating agent added to the polypropylene resin needs to be appropriately adjusted depending on the type of the β-crystal nucleating agent or the composition of the polypropylene-based resin. 0.0001 to 5.0 parts by mass of the agent is preferred. 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 ability can be obtained even when a laminated porous film is formed. Can be secured, and the 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.
In the present invention, the addition amount of the β crystal nucleating agent may be the same or different in each of the two layers. The porous structure of each layer can be appropriately adjusted by changing the addition amount of the β crystal nucleating agent.

In the PP-S layer, the total mass of the PP resin and the LM resin occupies 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more with respect to the total mass of the PP-S layer.
The mixing mass ratio of PP resin and LM resin is preferably PP resin / LM resin = 10 to 90/90 to 10, more preferably 20 to 80/80 to 20, and 30 to 70/70 to 30. Further preferred. Of these, a higher PP resin content is preferred, with PP resin / LM resin = 60-90 / 40-10 being more preferred, and 60-70 / 40-30 being even more preferred. When the content of the LM resin is less than 10% by mass in the total mass of 100% by mass of the PP resin and the LM resin, it becomes difficult to exhibit the shutdown characteristics at an appropriate temperature. On the other hand, if the content of the LM resin exceeds 90% by mass in 100% by mass of the total mass of the PP resin and the LM resin, it becomes difficult to make the PP-S layer porous.

When two or more PP-S layers are present, the mixing mass ratio of the PP resin and the LM resin in at least one of the layers may be within the specified range. The mixed mass ratio of the PP resin and the LM resin in the other PP-S layers is preferably PP resin / LM resin = 10 to 99/90 to 1, more preferably 30 to 99/70 to 1, 60-99 / 40-1 is still more preferable, and 60-90 / 40-10 is especially preferable.
Since it is sufficient that at least one layer exhibiting the shutdown characteristics is present, the shutdown characteristics are not necessarily required for the other PP-S layers. Therefore, the content of the LM resin may be 1% by mass or more in the total mass of 100% by mass of the PP resin and the LM resin. Of course, there is no problem even if all of the PP-S layer develops the shutdown characteristic, but that is preferable. On the other hand, if the content of the LM resin exceeds 90% by mass in 100% by mass of the total mass of the PP resin and the LM resin, it becomes difficult to make the PP-S layer porous.

In the PP-N layer, the content of the PP resin accounts for 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more with respect to the total mass of the PP-N layer.
In order to improve the mechanical strength, another thermoplastic resin may be combined with the PP resin.

Below, the component which comprises the said laminated porous film is demonstrated.
[Description of polypropylene resin (PP resin)]
Examples of polypropylene resins include homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Examples thereof include random copolymers with α-olefins and block copolymers. 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 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, when it exceeds 15 g / 10 minutes, the mechanical strength of the obtained laminated porous film is insufficient, and thus 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 aspect | 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, sebacic acid 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 LM resin]
Next, the LM resin will be described.
It is important that the LM resin has a crystal melting peak temperature of 100 to 150 ° C. By using such a thermoplastic resin, the laminated porous film of the present invention can exhibit appropriate shutdown characteristics described later.
Here, the crystal melting peak temperature of the thermoplastic resin means that the temperature is raised to 25 to 240 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter and held for 1 minute, and then cooled to 240 to 25 ° C. It refers to the crystal melting peak temperature that is detected when the temperature is held at 1 ° C./min and then held for 1 minute, and further raised to 25 to 240 ° C. at a heating rate of 10 ° C./min.

The LM resin is not particularly limited as long as it satisfies the crystal melting peak temperature condition.
Specifically, polyolefin resin such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene vinyl acetate copolymer, or polymethylpentene 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 can also be used.

  In particular, when considering use as a battery separator, a polyolefin resin, a mixture of polyolefin resins, or a mixture of a polyolefin resin and another thermoplastic resin is preferable as the LM resin from the viewpoint of chemical resistance and the like. In particular, the LM resin is 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 alone.

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 laminated porous film having an appropriate shutdown temperature is obtained. On the other hand, if it is 0.970 g / cm < ³ > or less, it will become a laminated porous film which has moderate shutdown temperature, and it is preferable at the point by which a drawability 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 the thermoplastic resin represented by the said polypropylene-type resin and a polyethylene-type resin is not specifically limited, For example, a well-known polymerization method using the well-known olefin polymerization catalyst, for example, a Ziegler-Natta type catalyst, Examples thereof include a polymerization method using a single site catalyst typified by a multi-site catalyst and a metallocene catalyst.

[Description of other ingredients]
In any of the two layers (PP-S layer and PP-N layer), in addition to the components described above, additives generally blended in the resin composition can be added as appropriate within a range that does not significantly impair the effects of the present invention. . 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.

  As long as the thermal characteristics of the laminated porous film, specifically, the shutdown characteristics are not impaired, the laminated porous film can be mixed with the polyolefin resin. Examples of the thermoplastic resin other than the LM resin include styrene resins such as styrene, AS resin, ABS resin, and PMMA resin: polyvinyl chloride, fluorine resin, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, and the like. Ester resins; Ether resins such as polyacetal, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, or polyphenylene sulfide; Thermoplastics such as polyamide resins such as 6 nylon, 6-6 nylon, and 6-12 nylon Resin.

  In addition, PP-S layers and PP-N layers are called rubber components such as thermoplastic elastomers as long as they do not impair the thermal characteristics of the laminated porous film, specifically, the shutdown characteristics. May be added. Examples of the thermoplastic elastomer include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.

The configuration of the laminated porous film of the reference embodiment is not particularly limited as long as at least a PP-S layer and a PP-N layer that are basic configurations exist . Within a range which does not impair the function of the product layer porous film may be laminated with other layers, it may be such as applying a per se known treatment as appropriate.
The simplest structure includes a two-layer structure of PP-S layer / PP-N layer. Next, a simple structure is a three-layer structure composed of two types, a PP-S layer and a PP-N layer. Specifically, PP-S layer / PP-N layer / PP-S layer, PP-N layer / PP-S layer / PP-N layer. In the case of the former configuration, the content of the LM resin in the two PP-S layers may be the same or different.
In addition, it is possible to adopt a form of three types and three layers in combination with layers having other functions. In this case, the stacking order of the PP-S layer, the PP-N layer, and the layer having other functions is not particularly limited.
Further, the number of layers may be increased as necessary to 4 layers, 5 layers, 6 layers, and 7 layers. When there are two or more PP-S layers, the content of the LM resin in each PP-S layer may be the same or different.
As a particularly preferred embodiment, a three-layer configuration of PP-N layer / PP-S layer / PP-N layer can be exemplified. By employing this three-layer structure, has a superior the air permeability properties and mechanical strength, and the laminated porous film provided with the shutdown characteristics can be more obtained more productivity, economical efficiency.

  Regarding the stacking ratio of the PP-S layer and the PP-N layer, the PP-N layer (the total thickness when there are two or more layers) / the PP-S layer (the total thickness when there are two or more layers) A value is 0.1-10, Preferably it is 0.3-5, More preferably, it is 0.5-3. If it is smaller than 0.1, the mechanical strength may not be sufficiently exhibited because the PP-N layer is substantially absent. On the other hand, when the value is larger than 10, it is difficult to ensure the safety of the battery from the viewpoint of insufficient shutdown characteristics. When other layers other than the PP-S layer and the PP-N layer are present, the total thickness of the other layers is 0.1 to 0.5, preferably 0.1. -0.3.

[Description of First Embodiment]
In the first embodiment of the laminated porous film of the present invention, the at least two porous layers are layers (PP-S layers) containing PP resin and LM resin, and the two PP-S layers The thermoplastic resin content is varied.
In the layer containing PP resin and LM resin (PP-S layer), the total mass of PP resin and LM resin is 70% by mass or more, preferably 80% by mass or more, more preferably, based on the total mass of PP-S layer. Occupies 90% by mass or more.
In the PP-S layer, an additive or a rubber component generally blended in the resin composition can be appropriately added within a range that does not significantly impair the effects of the present invention. Examples of the additive or rubber component include the same compounds as those mentioned in the first embodiment.

  Of the layers containing PP resin and LM resin (PP-S layer), the layer having the highest LM resin content (PP-Sm layer) has a mixed mass ratio of PP resin and LM resin of PP resin / LM. The resin is preferably 10 to 90/90 to 10, more preferably 20 to 80/80 to 20, and still more preferably 30 to 70/70 to 30. Of these, a higher PP resin content is preferred, with PP resin / LM resin = 60-90 / 40-10 being more preferred, and 60-70 / 40-30 being even more preferred. When the content of the LM resin is less than 10% by mass in the total mass of 100% by mass of the PP resin and the LM resin, it becomes difficult to exhibit the shutdown characteristics at an appropriate temperature. On the other hand, if the content of the LM resin exceeds 90% by mass in the total mass of 100% by mass of the PP resin and the LM resin, it becomes difficult to make the PP-Sm layer porous.

Among the layers containing PP resin and LM resin (PP-S layer), the layer having the smallest content of LM resin (PP-Sf layer) has a mixed mass ratio of PP resin and LM resin of PP resin / LM. The resin is preferably 50 to 99/50 to 1, more preferably 70 to 99/30 to 1, and still more preferably 90 to 99/10 to 1. When the content of the PP resin is less than 50% by mass in 100% by mass of the total mass of the PP resin and the LM resin, it becomes difficult to exhibit excellent mechanical strength.
Of the layer containing PP resin and LM resin (PP-S layer), the content (mass%) of LM resin in the layer having the highest content of LM resin (PP-Sm layer) and the content of LM resin The difference from the content (% by mass) of the LM resin in the layer having the smallest amount (PP-Sf layer) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass. .

The mixed mass ratio of the PP resin and the LM resin in the PP-S layer other than the PP-Sm layer and the PP-Sf layer is preferably PP resin / LM resin = 10 to 99/90 to 1, and preferably 30 to 99. / 70-1 are more preferable, 60-99 / 40-1 are still more preferable, and 60-90 / 40-10 are especially preferable.
Since at least one layer of the PP-Sm layer needs to be present as a layer that exhibits the shutdown characteristic, the shutdown characteristic is not necessarily required for the other PP-S layers. Therefore, the content of the LM resin may be 1% by mass or more in the total mass of 100% by mass of the PP resin and the LM resin. On the other hand, if the content of the LM resin exceeds 90% by mass in 100% by mass of the total mass of the PP resin and the LM resin, it becomes difficult to make the PP-S layer porous.

The configuration of the laminated porous film of the first embodiment is not particularly limited as long as at least a PP-Sm layer and a PP-Sf layer that are basic configurations exist.
The number of layers can be appropriately selected from 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, and 7 layers. However, a two-layer or three-layer structure is preferable from the viewpoint of productivity or economy.
Other layers may be laminated as long as the functions of the laminated porous film of the present invention are not hindered, or a process known per se may be appropriately performed.

The lamination ratio of each layer is not particularly limited, but the value of PP-Sf layer / PP-Sm layer is 0.1 to 10, preferably 0.3 to 5, more preferably 0.5 to 3. is there. If it is less than 0.1, the mechanical strength may not be sufficiently exhibited because the PP-Sf layer is substantially absent. On the other hand, when the value is larger than 10, it is difficult to ensure the safety of the battery from the viewpoint of insufficient shutdown characteristics. When other layers other than the PP-S layer are present, the total thickness of the other layers is 0.1 to 0.5, preferably 0.1 to 0.3, with respect to the total thickness 1. To be.
Since other components and effects are the same as those in the above-described reference embodiment, description thereof is omitted.

[Description of Shape and Physical Properties of Laminated Porous Film of Reference Embodiment and First Embodiment]
The form of the film of the reference embodiment and the first embodiment may be either a flat shape or a tube shape, but the productivity is good because several products can be taken in the width direction of the film-like material. further in view of possible Oh Rukoto such treatment such as coating the inner surface, flat it 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 the thickness 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, it is difficult to short-circuit and is safe. 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 ensured.

The physical properties of the laminated porous film of the present invention can be freely adjusted by the layer constitution, the lamination ratio, the composition of each layer, and the production method.
The laminated porous film of the present invention preferably exhibits a shutdown characteristic at a temperature exceeding 100 ° C. and not exceeding 160 ° C. That is, the shutdown temperature of the laminated porous film of the present invention is preferably more than 100 ° C. and 160 ° C. or less, more preferably 110 to 150 ° C., and further preferably 120 to 140 ° C.
For example, when left in a car in summer, there is a possibility that the temperature may be close to 100 ° C. depending on the location. It is preferable that the shutdown temperature is higher than 100 ° C., even in such a case, the micropores in the battery separator are retained and the lithium ion permeation function can be maintained as the separator. On the other hand, if it is 160 ° C. or lower, for example, when the battery becomes abnormal and becomes a high temperature state exceeding 100 ° C., the micropores of the porous film are immediately closed, and the permeation of lithium ions is blocked. Since the temperature rise inside the battery can be prevented, it is excellent in safety.
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 means for adjusting the shutdown temperature, it is effective to select an LM resin having a crystal melting peak temperature close to the desired shutdown temperature, or to increase the mass ratio of the LM resin in the PP-S layer.

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 2000 seconds / 100 ml. If the air resistance is greater than 10,000 seconds / 100 ml, the numerical value of the air resistance will be obtained in the measurement, but it means that the structure is quite poor in communication, so there may be substantially no communication. Many.
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.

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. When the porosity is 5% or more, it is possible to obtain a laminated porous film that ensures communication and has excellent air permeability. On the other hand, if the porosity is 80% or less, there is no problem that the number of fine holes increases and the mechanical strength of the film is lowered, which is preferable from the viewpoint of handling.
For example, as a means for increasing the porosity, there is a means for increasing the mass ratio of the LM resin in the PP-S layer, and a means for setting the stretching temperature to a lower temperature within the range defined by the present invention is effective. is there.
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 1 . And a 5N or more, more preferably more than 2.0 N, more preferably not less than 3.0 N.
The pin puncture strength is a value of breaking strength when a needle is pierced into the surface of the laminated porous film, and is a value serving as an index of mechanical strength of the film. Specifically, it is measured by the method described in the examples.
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 piercing strength is lower than 1.5N, the film is easily broken when contacting the metal edge or protrusion during battery production, and as a result, the probability of occurrence of a short circuit due to direct contact between the positive electrode and the negative electrode increases.
On the other hand, the upper limit value of the pin puncture strength is not particularly defined, but a value of 10 N or less is usually used from the viewpoint of handling.

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 the ratio of the tensile strength in the MD direction and the TD direction and the ratio of the tear strength in the MD direction and the 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.

[Description of Method for Producing Laminated Porous Film]
Next, although the manufacturing method of the lamination | stacking porous film of this invention is demonstrated, this invention is not limited only to the lamination | stacking porous film manufactured by this manufacturing method.
The manufacturing method of the laminated porous film of this invention is divided roughly into the following three by the order of porous formation and lamination.
(A) A method of laminating each porous layer after laminating each porous layer or bonding with an adhesive or the like.
(B) A method of laminating each layer to produce a laminated nonporous film-like material and then making the nonporous film-like material porous.
(C) After making any one of the two layers porous, a laminate is produced by a method of laminating with another layer of non-porous membrane or a method of adhering with an adhesive, etc. A method of making an object porous.
In the present invention, it is preferable to use the method (b) from the viewpoint of simplification of the process and productivity, and in particular, in order to ensure the interlayer adhesion between the two layers, a directly laminated nonporous film-like material is formed by coextrusion. A method of making it porous after production is particularly preferred.

The following manufacturing method is mentioned as a preferable aspect of the manufacturing method of the laminated porous film of this invention.
The laminated porous film of the reference embodiment includes a thermoplastic resin composition containing PP resin, β crystal nucleating agent and LM resin, and a thermoplastic resin containing PP resin and β crystal nucleating agent and no LM resin. Using the resin composition, a laminated nonporous film-like material composed of at least two layers of a PP-S layer and a PP-N layer is produced by coextrusion, and the laminated nonporous film-like material is stretched in the thickness direction. A method for producing a laminated porous film characterized in that a large number of fine pores having communication properties are formed.
As a method for producing the laminated porous film of the first embodiment, a thermoplastic resin composition containing two or more types of PP resin, β crystal nucleating agent and LM resin having different LM resin contents is used. A microporous material having connectivity in the thickness direction by producing a laminated nonporous membrane-like material comprising two or more PP-S layers having different LM resin contents by extrusion, and stretching the laminated nonporous membrane-like material And a method for producing a laminated porous film characterized by forming a large number of.
Moreover, also in the manufacturing method of reference embodiment and 1st Embodiment, in order to ensure the interlayer adhesiveness in coextrusion, it is preferable that PP ratio of each layer is 50 mass% or more.

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 manufactured by the tubular method and making it flat 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. Do. Among these, biaxial stretching is preferable from the viewpoint of controlling the porous structure.

Details of the manufacturing method of the first embodiment will be described below, but the manufacturing method of the second embodiment is exactly the same.
First, a thermoplastic resin composition containing a PP resin, a β crystal nucleating agent, and an LM resin that constitute the PP-S layer is prepared.
For example, raw materials such as polypropylene resin, β crystal nucleating agent, LM resin and other additives as required, preferably using a Henschel mixer, super mixer, tumbler type mixer, etc., or putting all ingredients in a bag After mixing by hand blending, the mixture is melt-kneaded with a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized.

Next, a thermoplastic resin composition that includes a PP resin and a β crystal nucleating agent that constitute the PP-N layer and does not include an LM resin is prepared.
For example, raw materials such as polypropylene resin, β crystal nucleating agent and other additives as required, preferably by using a Henschel mixer, a super mixer, a tumbler type mixer or the like, or put all ingredients in a bag for hand blending 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 PP-S layer resin composition and the PP-N layer resin composition pellets are put into separate extruders and extruded from a T-die co-extrusion die to form a film. The type of T die is not particularly limited. For example, when the laminated porous film of the present invention has a two-kind three-layer structure, the T die may be a two-kind three-layer multi-manifold type or a two-kind three-layer feed block type.
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 temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 180 to 300 ° C, and more preferably in the range of 200 to 280 ° C. A temperature of 180 ° C. or higher is preferable because the melted resin has a sufficiently low viscosity and excellent moldability. On the other hand, by setting the temperature to 300 ° C. or lower, it is possible to suppress deterioration of the resin composition, and hence reduction of the mechanical strength of the film.
The cooling and solidification temperature by the cast roll is very important in the present invention, and β crystal of PP resin can be generated and grown, and the ratio of β crystal of PP resin in the film can be adjusted. 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 solidifying 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, the β crystal ratio of the PP resin of the obtained film can be adjusted 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 of the film-like material before stretching to 30% or more, a porous film can be easily made porous by a subsequent stretching operation, and a laminated porous film having good air permeability can be obtained.
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. Among these, sequential biaxial stretching is more preferable because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled.

When sequential biaxial stretching is used, the stretching temperature must be appropriately selected depending on the composition of the resin composition used, the crystal melting peak temperature of the LM resin, the crystallinity of the PP resin, etc., but is selected within the range of the following conditions. It is preferable.
The stretching temperature in the longitudinal stretching is generally controlled in the range of 20 to 130 ° C, preferably 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 140 ° C. The transverse draw ratio is preferably 2 to 10 times, more preferably 3 to 8 times, and further preferably 4 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, and as a result, a laminated porous film having excellent air permeability characteristics. Can be obtained.
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. When the stretching speed is in this range, the laminated porous film of the present invention can be produced efficiently.

In the present invention, the stretching temperature in the sequential biaxial stretching satisfies the following formula in order to control the porosity in the stretching process and to exhibit excellent air permeability characteristics by forming an ideal porous structure. It is preferable to set so.
_{20 ℃ <T MD <T mLM} -20 ℃ <T TD
T _MD : Stretching temperature in longitudinal (MD) stretching, T _TD : Stretching temperature in transverse (TD) stretching, T _MLM : Crystal melting peak temperature of LM resin (when LM resin is a mixture of two or more thermoplastic resins) Is the crystal melting peak temperature of the resin with the lowest crystal melting peak temperature)

That it is preferred that the stretching temperature in the longitudinal stretching is _{20 ℃ <T MD <T mLM} -20 ℃, more preferably from _{30 ℃ <T MD <T mLM} -30 ℃, 40 ℃ <T MD <T mLM -35 More preferred is ° C. If 20 degreeC < _TMD , ie, the extending | stretching temperature in longitudinal stretching is 20 degreeC or more, since the fracture | rupture at the time of extending | stretching is suppressed and uniform extending | stretching is performed, it is preferable. On the other hand, when T _MD <T _MLM -20 ° C., that is, when the stretching temperature in longitudinal stretching is 20 ° C. or more lower than the crystal melting peak temperature of LM resin, it is due to pore formation in PP resin and interfacial peeling between PP resin and LM resin. Since two types of hole formation of hole formation occur, the hole formation can be performed efficiently. In addition, the pores formed in this way are not _easily blocked by the subsequent lateral stretching, and for example, even when the lateral stretching temperature is higher than the crystal melting peak temperature T _MLM of the LM resin, the air permeability characteristics can be expressed. And is very useful in production.

On the other hand, the stretching temperature in transverse stretching is T _mLM −20 ° C. <T _TD . That is, if the stretching temperature in the transverse stretching is 20 ° C. lower than the crystal melting peak temperature of the LM resin, the stretchability is excellent. Excellent. On the other hand, the upper limit of the stretching temperature is not particularly specified, but it is preferably not higher than the α-crystal melting peak temperature of the polypropylene resin, generally not higher than 160 ° C., preferably not higher than 150 ° C., and more preferably not higher than 140 ° C.

  The laminated porous film thus obtained is preferably subjected to heat treatment at a temperature of about 100 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 this 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 resistance is preferably 5 to 3000 seconds / 100 ml, more preferably 20 to 2000 seconds / 100 ml, still more preferably 50 to 1000 seconds / 100 ml, Most preferably, it is 50-500 seconds / 100m.
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. There is often no degree of connectivity. 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 laminated porous film can be maintained.
The air permeation resistance represents the difficulty of air passing through in the thickness direction of the separator, and is specifically expressed by the number of seconds required for 100 ml of air to pass through the separator. 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 that the separator in the thickness direction is better, and a larger value means that the separator is less in the thickness direction. Communicability is the degree of connection of holes in the thickness direction of the separator. The low air permeability resistance of the lithium ion battery separator of the present invention means that lithium ions can be easily transferred, which is preferable because of excellent battery performance.

  When the laminated porous film of the present invention is used as a battery separator, the porosity is preferably 30 to 70%, more preferably 40 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 into a predetermined battery can and thus 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 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. In other words, lithium graphite oxide (LiCoO ₂ ) was 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 were 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, Reference Example, shows the actual施例and comparative examples, will be explained in detail the laminated porous film of the present invention, the present invention is not limited thereto.
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)
As shown in Table 1, the raw materials of the first layer (I) were transferred to the same direction biaxial extruder (caliber 40 mmφ, L / D = 32) manufactured by Toshiba Machine Co., Ltd., and the raw materials of the second layer (II). Is fed into the same type twin-screw extruder in the same direction, melted and mixed at 240 ° C., and then extruded from a T-die through a single-layer, 2-type 2-layer or 2-type 3-layer feed block according to the layer structure shown in Table 1. Then, the film was taken up with a cast roll having the temperature shown in Table 1 and cooled and solidified to obtain an unstretched film-like material having a width of 300 mm and a thickness of 180 μm. At this time, the (cooling) contact time between the molten resin film and the cast roll was 12 seconds.
Next, the obtained unstretched film-like material was stretched in the longitudinal direction at a stretching temperature and a stretching ratio shown in Table 1 between rolls using a film roll longitudinal stretching machine, and then a film manufactured by Kyoto Machine Co., Ltd. In a tenter facility, the film was stretched in the transverse direction at the stretching temperature and stretch ratio shown in Table 1. Furthermore, thermal relaxation was performed under the conditions described in Table 1 to obtain a laminated porous film.

The raw materials used in Examples and Comparative Examples are as follows.
In addition, about each polypropylene resin (PP-1, (beta) PP-1, (beta) PP-2), it heats from 25 degreeC to 240 degreeC using the differential scanning calorimeter (DSC-7) by Parkin Elmer. The temperature is raised at a rate of 10 ° C./min and held for 1 minute, then the temperature is lowered from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C./min. Whether or not a crystal melting peak (Tmβ) derived from the β crystal is detected in the range of 145 ° C. or higher and lower than 160 ° C. when the temperature is increased again is described.

(A) Polypropylene resin / PP-1: “Prime PP F300SV (trade name)” manufactured by Prime Polypro (MFR 3.0 g / 10 min, Tm 167 ° C., density 0.89 g / cm ³ )
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), each raw material is hand blended. , Put into a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (caliber 40 mmφ, L / D = 32), melt and mix at a preset temperature of 240 ° C., cool and solidify the strand in a water bath, and cut the strand with a pelletizer A mixed pellet of a polypropylene resin (PP-1) and a 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) Polyethylene resin PE-1: High-density polyethylene “Hi-Zex HZ2200J (trade name)” manufactured by Prime Polymer Co., Ltd.
(MFR 5.2 g / 10 min, Tm 134 ° C., density 0.964 g / cm ³ )
-PE-2: Ube Industries, Ltd. linear low density polyethylene "Umerit 3540F (trade name)"
(MFR 4.0 g / 10 min, Tm 123 ° C., density 0.931 g / cm ³ )
-PE-3: Linear Polyethylene “Carnell KF260 (trade name)” manufactured by Japan Polytechnic Co., Ltd.
(MFR 2.0 g / 10 min, Tm 93 ° C., density 0.903 g / cm ³ )

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

(1) Layer ratio The cross section of the laminated porous film was cut out and observed with a scanning electron microscope (SEM), and the layer ratio was measured from the layer configuration and thickness.

(2) Shutdown temperature The obtained film was cut into a 60 mm long × 60 mm wide 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. It should be noted that at 100 ° C., the gas resistance not exceeding 10 times that before heating is judged as “over 100 ° C.”, and at 160 ° C., the gas permeability resistance exceeding 10 times before heating is determined as “160 ° C. It was judged as follows.
In the present invention, the shutdown temperature is preferably more than 100 ° C. and 160 ° C. or less, and thus the evaluation was performed as follows.
○: Shutdown temperature exceeds 100 ° C and 160 ° C or less ×: Shutdown temperature is 100 ° C or less, or exceeds 160 ° C Note that if the film piece cannot be cut into a 60 mm x 60 mm square, a 40 mmΦ circular shape is formed at the center. The sample may be prepared by adjusting so that the film is placed in the hole.

(3) 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.
“◎” when the pin puncture strength is 3.0N or more, “◯” when the pin puncture strength is 1.5N or more and less than 3.0N, and “X” when the pin puncture strength is less than 1.5N. It was evaluated.

(4) Air resistance (Gurley value)
The air resistance (second / 100 ml) was measured according to JIS P8117.
When the air permeability resistance is 500 seconds / 100 ml or less, “◎”, when the air resistance exceeds 500 seconds / 100 ml and less than 2000 seconds / 100 ml, “◯”, and the air resistance is 3000 seconds / 100 ml. The case where it exceeded was evaluated as "x".

(5) Thickness A thickness of 1/1000 mm was used to measure 30 in-plane thicknesses unspecified, and the average was taken as the thickness.

(6) Porosity The porosity is a numerical value indicating the proportion of the space portion in the porous film. The porosity was determined by measuring the substantial amount W1 of the porous 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

(7) 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.

(8) β-crystal forming power As in the case of the measurement of the shutdown temperature, the film was cut into a 60 mm length × 60 mm square and fixed as shown in FIGS.
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.

The laminated porous films of the examples configured within the range specified in the present invention are superior in air permeability characteristics and mechanical properties as compared with the porous films of comparative examples configured in the range other than specified in the present invention. It can be seen that it has strength and also has a shutdown characteristic.
On the other hand, from Comparative Example 1, a thermoplastic resin other than the LM resin, specifically, a thermoplastic resin having a crystal melting peak temperature of 100 ° C. or less is added to a polypropylene resin having β activity and / or β crystal forming ability. In this case, it is understood that the shutdown characteristic is not exhibited in an appropriate temperature range, and the air permeability characteristic is also deteriorated.
From Comparative Example 2, it can be seen that when no LM resin is added, the shutdown characteristic does not appear in an appropriate temperature range.
From the comparative example 3, it turns out that the mechanical strength of the laminated porous film obtained is low only by the layer (PP-S layer) containing PP resin and LM resin.

  Since the laminated porous film of the present invention has excellent air permeability and mechanical strength and has shutdown characteristics, it can be suitably used for a battery separator.

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

Claims (10)

A laminated porous film in which at least two porous layers are laminated,
The two layers include a polypropylene resin having β activity and a thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C.
Among the layers containing the polypropylene resin and the thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C., in the layer having the smallest thermoplastic resin content, the polypropylene resin and the thermoplastic resin And the mixing mass ratio is the polypropylene resin / the thermoplastic resin = 90 to 99 / 10-1,
In the layer having the largest content of the thermoplastic resin, the mixing mass ratio of the polypropylene resin and the thermoplastic resin is the polypropylene resin / the thermoplastic resin = 20 to 80/80 to 20,
A laminated porous film having an air permeability resistance of 5 to 3000 seconds / 100 ml and a pin penetration strength of 1.5 N or more. A laminated porous film in which at least two porous layers are laminated,
The two layers include a polypropylene resin and a thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C.
Among the layers containing the polypropylene resin and the thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C., in the layer having the smallest thermoplastic resin content, the polypropylene resin and the thermoplastic resin And the mixing mass ratio is the polypropylene resin / the thermoplastic resin = 90 to 99 / 10-1,
In the layer having the largest content of the thermoplastic resin, the mixing mass ratio of the polypropylene resin and the thermoplastic resin is the polypropylene resin / the thermoplastic resin = 20 to 80/80 to 20,
A laminated porous film having β activity and / or β crystal forming power, air permeability resistance of 5 to 3000 seconds / 100 ml, and pin piercing strength of 1.5 N or more. The lamination according to claim 1 or 2, wherein a β crystal nucleating agent is blended in a composition forming at least one of the two layers to have the β activity and / or the β crystal generation ability. Porous film. Wherein the polypropylene resin of at least one layer of the two layers by blending a β-crystal nucleating agent, the β activity and / or the β crystal of any one of claims 1 to 3 are assumed to have a generation force The laminated porous film according to 1. The laminated porous film according to claim 4 , 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 laminated porous film according to any one of claims 1 to 5 , wherein the thermoplastic resin having a crystal melting peak temperature of 100 to 150 ° C is a polyethylene resin. The laminated porous film according to any one of claims 1 to 6 , wherein a shutdown temperature at which the pores are closed is 141 ° C or higher and 160 ° C or lower. The laminated porous film according to any one of claims 1 to 7 , wherein the porosity is 40 to 65%. A battery separator comprising the laminated porous film according to any one of claims 1 to 8 . A battery comprising the battery separator according to claim 9 incorporated therein.

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