JP5690794B2 - Method for producing laminated porous film - Google Patents

Description

The present invention relates to a method for producing a laminated porous film , and the produced laminated porous film is used as a packaging product, sanitary product, livestock product, agricultural product, building product, medical product, separation membrane, light diffusion plate, battery separator. In particular, it can be suitably used as a separator for non-aqueous electrolyte batteries.

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

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

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

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

  Another characteristic that contributes to safety is a breakdown characteristic (hereinafter referred to as “BD characteristic”). This BD characteristic is a function in which heat generation does not stop due to the development of the SD characteristic, and the film does not break even when the temperature is higher (160 ° C. or higher) and keeps the positive electrode and the negative electrode separated. If it has BD characteristics, insulation can be maintained even at high temperatures, and a wide range of short-circuits between electrodes can be prevented, thereby preventing accidents such as ignition due to abnormal heat generation of the battery. Therefore, when used as a battery separator, it is preferable that this BD characteristic is also provided, and the breakdown temperature is preferably higher.

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

  On the other hand, various methods for obtaining a porous film by stretching a polypropylene sheet containing β crystals have been proposed. A feature of this method for producing a porous film is that a porous structure is obtained by using β crystals, and it is preferable that a lot of β crystals are contained in the sheet before stretching to obtain a porous structure. In addition, this method is a general biaxial stretching method, and is characterized in that productivity is very good as a method for obtaining a porous film.

  For example, in Japanese Patent No. 1953202 (Patent Document 2), a manufacturing method for obtaining a porous film by forming a sheet of a resin composition containing a predetermined amount of a filler and a β-crystal nucleating agent in polypropylene and stretching the resin composition under specific stretching conditions. Has been proposed. In addition, Japanese Patent No. 2509030 (Patent Document 3) proposes a superporous polypropylene microporous film obtained by biaxial stretching from an original polypropylene film having a high β crystal content (K> 0.5). . In Japanese Patent No. 3443934 (Patent Document 4), a specific amide compound is contained in polypropylene, and crystallized under specific conditions to obtain a solidified product containing β crystals. A method for producing a film has been proposed.

  These polypropylene porous films are superior to the polyethylene porous film in BD characteristics because of the high crystal melting temperature of polypropylene. However, since the above characteristics are adversely affected and the SD characteristics cannot be exhibited at all, there is a problem in securing the safety of the battery in order to use these porous films as battery separators.

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

The present invention has been made in view of the above problems, while having a breakdown (BD) properties of the polypropylene resin, the production of porous film having both even a shutdown (SD) properties for ensuring the safety of the battery The challenge is to provide a method .

In order to solve the above problems, the present invention provides:
a layer (PP layer) made of a polypropylene resin containing a β crystal nucleating agent and having β activity and / or β crystal generation ability;
A peak value of the crystal melting temperature is lower than that of the polypropylene-based resin, and a thermoplastic resin composition containing a thermoplastic resin and a barium sulfate having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower is used. in consists of at least two layers of a layer shutdown (SD layer), the shutdown temperature hole is closed is prepared Oh Ru laminated unporous membrane material at 0.99 ° C. or less exceed 100 ° C.,
A method of making the SD layer porous is a filler method,
There is provided a method for producing a laminated porous film, characterized in that a number of micropores having communication in the thickness direction are formed by biaxially stretching the laminated nonporous film-like material.
It is preferable that the PP layer and the SD layer are laminated in two layers and three layers in the coextrusion step.
The thermoplastic resin composition of the SD layer including barium sulfate as a filler.

The shutdown layer (SD layer) is composed of a resin composition having a crystal melting peak temperature lower than the crystal melting peak temperature of the resin composition of the PP layer, and has a shutdown temperature lower than that of the PP layer, It is formed using a thermoplastic resin composition containing a thermoplastic resin having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower, and a shutdown temperature at which pores are blocked is higher than 100 ° C. and 150 ° C. or lower.
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.

The PP layer of the laminated porous film produced by the production method of the present invention (hereinafter abbreviated as “laminated porous film of the present invention”) is blended with a β crystal nucleating agent to produce β activity and / or β crystals. Since it has force, a fine porous layer can be provided, and excellent air permeability characteristics can be exhibited.
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 laminated in any case where the laminated porous film of the present invention is composed of only the PP layer and the SD layer, and when another porous layer is laminated. It is measured in the state of a porous film.

The laminated porous film, by incorporating β-crystal nucleating agent to the resin composition of the PP layer, it is assumed to have the β activity and / or the β crystal generation power.
By incorporating a β-crystal nucleating agent prior Symbol polypropylene resin, the PP layer is assumed to have the β activity and / or the β crystal generation power. 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.

The SD layer is a layer having a shutdown temperature lower than that of the PP layer, includes a thermoplastic resin having a crystal melting peak temperature of 100 ° C. or more and 150 ° C. or less, and has a shutdown temperature exceeding 100 ° C. and 150 ° C. Ru der below.
The “thermoplastic resin having a crystal melting peak temperature of 100 ° C. or more and 150 ° C. or less” is a resin different from the polypropylene resin of the PP layer and a differential scanning calorimeter according to JIS K7121. When the temperature is raised from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min, the peak value of the crystal melting temperature detected is 100 ° C. or more and 150 ° C. or less, and is a polyethylene resin. Is preferred.
The SD layer is preferably a layer containing a filler, and an inorganic filler is preferred as the filler.

The laminated porous film of the present invention preferably has an air permeability resistance of 1 to 10000 seconds / 100 ml.
Furthermore, the pin puncture strength is preferably 1.5 N or more.
The air permeation resistance and the pin puncture strength are measured by the methods described in Examples described later.

Product layer porous film produced by the production method of the present invention, air resistance is preferably used as a battery separator is 5 to 3000 sec / 100 ml, batteries in which the separator is incorporated and is highly safe battery Become.

The laminated porous film produced by the production method of the present invention is a laminated porous film in which at least two porous layers are laminated, and one of the porous layers is a layer (PP layer) containing a polypropylene resin. The other layer is made of a composition having a crystal melting peak temperature lower than the crystal melting peak temperature of the resin composition of the layer containing the polypropylene resin, and the shutdown temperature is higher than 100 ° C. and lower than 150 ° C. Since it is a layer (SD layer), it has a shutdown characteristic in which the pores are closed in an appropriate temperature range while maintaining the breakdown temperature of the conventional laminated porous film made of polypropylene resin.
Furthermore, since the laminated porous film produced by the production method of the present invention has β activity and / or β crystal generation power, it has fine pores and can ensure sufficient communication, and the PP layer Since the strength can be maintained, the mechanical strength such as pin puncture strength and tear strength is excellent. Therefore, it is useful for battery separators from the viewpoint of structure maintenance and impact resistance.
Moreover, the manufacturing method of the lamination | stacking porous film of this invention does not require exact | strict control of manufacturing conditions, but can produce it simply and efficiently.

It is a partially broken perspective view of a non-aqueous electrolyte battery containing a laminated porous film manufactured by the manufacturing method of the present invention as a battery separator. (A) (B) is a figure explaining the restraint method of the film in the measurement of SD characteristic in an Example, BD characteristic, and (beta) crystal formation power.

Hereinafter, embodiments of the laminated porous film produced by the production method of the present invention will be described in detail.
The produced laminated porous film is a laminated porous film in which at least two porous layers are laminated, and one of the two porous layers is a layer containing a polypropylene resin (PP layer). The other porous layer is a shutdown layer (SD layer) made of a resin composition having a crystal melting peak temperature lower than the crystal melting peak temperature of the resin composition of the layer containing the polypropylene resin, and the laminated porous film Has β activity and / or β crystal-forming ability.

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 force can be regarded as one index indicating that polypropylene was generating β crystal in the film-like material before stretching. If the polypropylene in the film-like material before stretching produces β crystals, fine pores are formed by subsequent stretching, so that a separator having air permeability can be obtained.

The presence or absence of β activity of the laminated porous film can be determined by conducting a differential thermal analysis of the laminated porous film using a differential scanning calorimeter and detecting a crystal melting peak temperature derived from β crystals of polypropylene resin. Judgment is based on no.
Specifically, the laminated porous film is heated at a heating rate of 10 ° C./min from 25 ° C. to 240 ° C. for 1 minute with a differential scanning calorimeter, and then cooled from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C. / When the temperature is lowered for 1 minute and held for 1 minute, and when the temperature is raised again from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./minute, the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene is If detected, 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, in the case of homopolypropylene, the heat of crystal melting derived from β crystal (ΔHmβ) detected mainly in the range of 145 ° C. or higher and lower than 160 ° C. and the α crystal derived from α crystal detected mainly at 160 ° C. or higher and 175 ° C. or lower. It can be calculated from the heat of crystal fusion (ΔHmα). Further, for example, in the case of random polypropylene copolymerized with 1 to 4 mol% of ethylene, the crystal melting heat amount (ΔHmβ) derived from the β crystal detected mainly in the range of 120 ° C. or more and less than 140 ° C., and mainly 140 It can be calculated from the crystal melting calorie (ΔHmα) derived from the α crystal detected in the range of from 0 ° C. to 165 ° C.

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

The presence or absence of the β crystal generation force is determined by a diffraction profile obtained by wide-angle X-ray measurement of a laminated porous film subjected to a specific heat treatment.
Specifically, a wide-angle X-ray measurement was performed on a separator for a lithium ion battery that was subjected to heat treatment at 170 to 190 ° C., which is a temperature exceeding the melting point of the polypropylene 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 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.

In the present invention, the PP layer is obtained by adding a β crystal nucleating agent to obtain β activity and / or β crystal generation ability . By adding a β crystal nucleating agent, lithium ions having a porous layer having β activity and / or β crystal generation ability can be promoted more uniformly and efficiently to generate β crystals of polypropylene resin. A battery separator can be obtained .

Below, the detail of the component of each layer which comprises the laminated porous film manufactured with the manufacturing method of this invention is demonstrated.

[Description of PP layer]
First, the PP layer will be described in detail below.
(Description of polypropylene resin)
Polypropylene resins contained in the PP layer include homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene. Alternatively, a random copolymer or block copolymer with an α-olefin such as 1-decene may be mentioned. Among these, homopolypropylene is more preferably used from the viewpoint of the mechanical strength of the laminated porous film.

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

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

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

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

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

下記式（ｂ）；

下記式（ｃ）；

または、下記式（ｄ）；

で示される基を表す。化学式１〜４において、Ｒ_４およびＲ_５は同一または異なって水素原子、炭素数１〜１２の直鎖状または分岐鎖状のアルキル基、Ｒ_６およびＲ_７は同一または異なって炭素数１〜１２の直鎖状または分岐状のアルキレン基を表す。）
で示される化合物である。 Among them, as the amide compound represented by the general formula (I), (II), or (III), an amide compound represented by the general formula (1), (2), or (3) is particularly preferable. It is mentioned as one aspect | mode.
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鎖状のアルキル基、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の直鎖状も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 chain having 1 to 12 carbon atoms. 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, and R ₅₁ is a hydrogen atom, a carboxyl group, or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom, a carboxyl group, or a carbon number of 1). Represents a -12 linear or branched alkyl group, 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.

  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 at the time of production, and sufficient β-activity and / or β-crystal-forming power can be secured. In addition, sufficient β activity and / or β crystal forming power can be secured, and desired air permeability and mechanical strength can be obtained. On the other hand, 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 film surface.

The PP layer is made of a polypropylene resin blended with a β crystal nucleating agent .

[Description of Shutdown Layer (SD Layer)]
Next, the SD layer will be described.
The SD layer of the present invention is a porous layer composed of a composition having a lower crystal melting peak temperature than the resin composition of the PP layer, and includes a thermoplastic resin having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower. This is a porous layer using a plastic resin composition and having a shutdown temperature at which the pores are blocked exceeding 100 ° C. and not exceeding 150 ° C.

The SD layer has a large number of fine pores communicating in the thickness direction, and has a crystal melting peak temperature (crystal melting peak temperature of 100 ° C. or more and 150 ° C. or less) lower than the composition of the PP layer as described above . is composed of a thermoplastic resin composition comprising a resin, as long as the shutdown temperature is below 0.99 ° C. beyond 100 ° C., it may be any structure and composition. For example, it may have a structure in which the fine pores are provided in a film-like material made of a thermoplastic resin composition, or particulate or fibrous fine objects aggregate to form a layer, A structure in which the gap is the fine hole may be used. The SD layer of the present invention preferably has the former structure in which uniform fine pores can be formed and the porosity and the like can be easily controlled.

The thermoplastic resin composition that make up the SD layer, the thermal properties are important. That is, it is necessary to select the thermoplastic resin so that the crystal melting peak temperature of the composition constituting the SD layer is lower than the crystal melting peak temperature of the composition constituting the PP layer. Therefore, the SD layer contains a thermoplastic resin having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower .
This crystal melting peak temperature is a peak value of the crystal melting temperature when the temperature is raised from 25 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter in accordance with JIS K7121.

The thermoplastic resin having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower is not particularly limited as long as the crystal melting peak temperature is satisfied.
When considering use as a battery separator, from the viewpoint of chemical resistance, 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 (A) can also be used.

In this case, the above-mentioned mixing of polyolefin resins or the mixing of polyolefin resins and other thermoplastic resins is preferable, and the mixing of polyolefin resins is particularly preferable.
Examples of the thermoplastic resin having a crystal melting peak temperature of 100 ° C. or more and 150 ° C. or less include polyethylene resins such as low density polyethylene, high density polyethylene, and linear low density polyethylene, or polyethylene resins and other polyolefin resins. And a polyethylene resin alone is still more preferable.

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 an SD layer having an appropriate shutdown temperature can be formed. On the other hand, 0.970 g / cm ³ or less is preferable in that a laminated porous film having an SD layer having an appropriate shutdown temperature can be formed, and stretchability is maintained. The density can be measured according to JIS K7112 using a density gradient tube method.

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

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

  If necessary, in the SD layer, a mixture of two or more kinds of resins may be used as long as the thermal characteristics of the laminated porous film, specifically, the SD characteristics are not impaired. Examples of other thermoplastic resins that can be mixed with the aforementioned polyolefin resins include styrene resins such as styrene, AS resin, ABS resin, or PMMA resin: polyvinyl chloride, fluorine resin, polyethylene terephthalate, polybutylene terephthalate. Ester resins such as polycarbonate or polyarylate; ether resins such as polyacetal, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone or polyphenylene sulfide; 6 nylon, 6-6 nylon, 6-12 nylon, etc. Examples thereof include thermoplastic resins such as polyamide-based resins.

  Moreover, you may add what is called rubber components, such as a thermoplastic elastomer, to the resin composition which comprises SD layer as needed. Examples of the thermoplastic elastomer include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.

The SD layer may contain a substance that promotes porosity. It is particularly preferable to add a filler to the SD layer. By inserting a filler, a porous structure can be obtained more efficiently and the shape of the pores can be easily controlled.
As the filler, either an inorganic filler or an organic filler can be used, and one kind or a combination of two or more kinds can be used. Especially, it is preferable to use an inorganic filler from the viewpoint of heat resistance and the like.
In the present invention, the resin composition constituting the SD layer contains at least barium sulfate as a filler.

  Examples of inorganic fillers include carbonates such as calcium carbonate, magnesium carbonate and barium carbonate; sulfates such as calcium sulfate, magnesium sulfate and barium sulfate; chlorides such as sodium chloride, calcium chloride and magnesium chloride; aluminum oxide, oxidation In addition to oxides such as calcium, magnesium oxide, zinc oxide, titanium oxide, and silica, silicates such as talc, clay, and mica can be used. Among these, barium sulfate which has low solubility in an electrolytic solution when used as a battery separator is preferable.

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

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

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

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

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

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

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

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

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

  In addition, the SD layer may be blended with additives or the like generally blended into the resin composition within a range that does not impair the object of the present invention and the characteristics of the SD layer. Specifically, it is the same as the example of the additive which can be mix | blended with PP layer.

[Description of laminated structure]
The laminated structure of the laminated porous film of the present invention will be described.
There is no particular limitation as long as there is at least a PP layer and an SD layer, which are basic structures. The simplest structure is a two-layer structure of a PP layer and an SD layer, and then the simplest structure is a two-kind three-layer structure of both an outer layer and an intermediate layer, which are preferable structures. In the case of two types and three layers, it may be a PP layer / SD layer / PP layer or an SD layer / PP layer / SD layer. In addition, it is possible to adopt a form of three types and three layers in combination with layers having other functions as required. Further, the number of layers may be increased as necessary to 4 layers, 5 layers, 6 layers, and 7 layers.
About the lamination | stacking ratio of PP layer and SD layer, the value of PP layer / SD layer is 0.1-10, Preferably it is 0.3-5, More preferably, it is 0.5-3. When it is smaller than 0.1, the BD characteristic and strength cannot be sufficiently exhibited because the PP layer is substantially absent. On the other hand, when it is larger than 10, it is difficult to ensure safety from the viewpoint that the SD characteristic is insufficient when applied to a battery, for example. When other layers other than the SD layer and PP 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.

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

The physical properties of the laminated porous film of the present invention can be freely adjusted by the composition of the PP layer or SD layer, the number of laminated layers and the lamination ratio, combinations with layers having other properties, and the production method.
The greatest feature of the laminated porous film of the present invention is that SD characteristics are exhibited at temperatures exceeding 100 ° C. and not exceeding 150 ° C. That is, the shutdown temperature of the laminated porous film of the present invention is more than 100 ° C. and 150 ° C. or less, preferably 110 to 145 ° C., more preferably 120 to 140 ° C. When shutdown occurs at 100 ° C. or lower, for example, when the laminated porous film of the present invention is used as a battery separator and the battery is left in a car in summer, the temperature becomes close to 100 ° C. depending on the location. Since there is a possibility, it is not preferable that the battery does not function in this state. On the other hand, the temperature higher than 150 ° C. is not sufficient in terms of ensuring safety as a battery.
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.
Effective means for adjusting the shutdown temperature include selecting a thermoplastic resin having a crystal melting peak temperature close to the desired shutdown temperature as the thermoplastic resin contained in the SD layer, and increasing the layer ratio of the SD layer. It is.

The laminated porous film of the present invention is also characterized by exhibiting BD characteristics at 160 ° C. or higher. That is, the breakdown temperature of the laminated porous film of the present invention is 160 ° C. or higher, preferably 200 ° C. or higher, more preferably 250 ° C. or higher. When the breakdown temperature is less than 160 ° C., there is no difference between the shutdown temperature and the breakdown temperature. For example, when the laminated porous film of the present invention is used as a battery separator, it is possible to provide a battery with sufficiently secured safety. Can not. On the other hand, although there is no restriction | limiting in particular about the high temperature side of breakdown temperature, Preferably it is 300 degrees C or less.
Here, the “breakdown temperature” refers to the lowest temperature among the temperatures at which the laminated porous film of the present invention breaks when heated by the method described in the examples.
As a means for adjusting the breakdown temperature, a means for increasing the layer ratio of the PP layer is effective.

The air-permeable resistance of the laminated porous film of the present invention is 1 to 10,000 seconds / 100 ml, preferably 5 to 3000 seconds / 100 ml, and more preferably 10 to 1000 seconds / 100 ml. If the air resistance is greater than 10,000 seconds / 100 ml, the numerical value of the air resistance 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. On the other hand, if it is less than 1 second / 100 ml, the porous structure becomes rough and the pore diameter becomes too large, which is not preferable.
The air permeation resistance represents the difficulty of air passage in the film thickness direction, and is specifically expressed in the number of seconds required for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means poor communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction. If the air permeability resistance of the laminated porous film of the present invention is low, it can be used for various applications. For example, when used as a separator of a lithium ion secondary battery, a low air permeability resistance means that lithium ions can be easily transferred, which is preferable because the battery performance is excellent.

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

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

In the laminated porous film of the present invention, the value of the heat shrinkage rate is preferably 15% or less in both the vertical direction and the horizontal direction, more preferably 10% or less.
In particular, when the laminated porous film of the present invention is used as a battery separator, it is preferable that the thermal shrinkage rate is small in order to ensure the safety of the battery, and if the thermal shrinkage rate exceeds 15%, the positive electrode inside the battery Therefore, it is difficult to provide a battery with high safety.
The thermal shrinkage rate is measured by the method described in the examples.

Moreover, in the laminated porous film of this invention, it is preferable that the anisotropy is small from a viewpoint of film physical property. As an anisotropy index, it can be expressed by a ratio of tensile strength in the MD direction (take-off (flow) direction) and TD direction (perpendicular to MD) or a ratio of tear strength in the MD direction and TD direction.
For example, taking tensile strength as an example, the lower limit value of the “MD strength / TD strength ratio” is 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more as a ratio of the ratio. . If the “MD strength / TD strength ratio” is 0.05 or more, the physical properties are balanced, and in addition to handling, the porous structure finally has a smaller anisotropy film. Further, the upper limit value of the “MD strength / TD strength ratio” is 20 or less, preferably 10 or less, more preferably 7 or less. If the “MD strength / TD strength ratio” is 20 or less, the physical properties are balanced, and in addition to handling, the porous structure finally has a smaller anisotropy film.
The measuring method of the tensile strength is measured according to JIS K7127. Specifically, both MD and TD were measured at a width of 15 mm, a length of 150 mm, a distance between evaluation points of 50 mm, a distance between chucks of 70 mm, and a crosshead speed of 200 mm / min. Indicates strength.
The MD tensile strength is 50 MPa or more, preferably 100 MPa or more, more preferably 120 MPa or more. If it is 50 MPa or more, it is sufficient strength when handling the film. Although there is no particular upper limit, a range in which the balance with TD tensile strength does not deviate from the above range is preferable.
The TD tensile strength is 50 MPa or more, preferably 100 MPa or more, more preferably 120 MPa or more. If it is 50 MPa or more, it is sufficient strength when handling the film. Although there is no particular upper limit, a range in which the balance with the MD tensile strength does not deviate from the above range is preferable.

[Description of manufacturing method]
The manufacturing method of the laminated porous film of this invention is demonstrated.
The method for producing a laminated porous film of the present invention comprises a layer made of a polypropylene resin that has a β-crystal nucleating agent and has β activity and / or β crystal-forming ability,
A peak value of the crystal melting temperature is lower than that of the polypropylene-based resin, and a thermoplastic resin composition containing a thermoplastic resin and a barium sulfate having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower is used. in consists of at least two layers of a layer shutdown (SD layer), laminated shutdown temperature which hole is closed consists of at least two layers of Oh Ru layers below 0.99 ° C. exceed 100 ° C. (SD layer) Muanamaku A method for producing a porous material and making the SD layer porous is a filler method, and then biaxially stretching the laminated non-porous membrane material to form a large number of fine pores having connectivity in the thickness direction. .

In the production method, a nonporous film PP containing a polypropylene resin having β activity and a non-porous film PP comprising a composition having a crystal melting peak temperature lower than a crystal melting peak temperature of the composition of the nonporous film PP. A porous membrane-like material SD was prepared, and the non-porous membrane-like material PP and the non-porous membrane-like material SD were laminated and then stretched or made porous, or the laminated non-porous membrane-like material was directly produced by coextrusion. there is a way to post-porous reduction. In the present invention, a method using coextrusion is particularly preferred from the viewpoint of simplicity of the process and productivity.

The production method of the laminated porous film of the present invention can also be classified according to the method of making the SD layer porous.
That, PP layer because it has a β activity and / or β crystal generation power, it is possible to easily form the micropores by biaxial stretching. On the other hand, it is preferable to use a full filler method the method of porous the SD layer.

The filler method is to form a non-porous layer or a non-porous film using a composition in which a resin is mixed with a filler, and to form micropores by peeling the interface between the resin and the filler by biaxial stretching. method Ru der.

As described above, the method for producing a laminated porous film of the present invention includes a layer made of a polypropylene resin containing a β crystal nucleating agent and having β activity and / or β crystal generation power,
A peak value of the crystal melting temperature is lower than that of the polypropylene-based resin, and a thermoplastic resin composition containing a thermoplastic resin and a barium sulfate having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower is used. in consists of at least two layers of a layer shutdown (SD layer), laminated shutdown temperature which hole is closed consists of at least two layers of Oh Ru layers below 0.99 ° C. exceed 100 ° C. (SD layer) Muanamaku The filler method is a method for producing a porous material and making the SD layer porous, and then forming a large number of fine pores having communication in the thickness direction by biaxially stretching the laminated non-porous membrane material. is there.

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.
As the stretching method of the laminated unporous membrane material, the present invention uses a biaxially oriented from the viewpoint of the multi-hole structure control.

  As a more preferred embodiment, a thermoplastic resin composition containing a polypropylene resin having β activity and / or β crystal forming power constituting the PP layer, and the polypropylene resin constituting the SD layer. Two-layer, three-layer laminated non-porous structure by T-die coextrusion so that a thermoplastic resin composition in which a filler is blended with a thermoplastic resin having a low peak value of crystal melting temperature is made porous by the filler method. A method for producing a laminated porous film in which a film-like material is produced and made porous by biaxially stretching the laminated nonporous membrane-like material will be described below.

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

  When preparing the resin composition constituting the SD layer, the raw materials such as the thermoplastic resin, filler, plasticizer and other additives as described in the description of the SD layer are used, and the Henschel mixer, super mixer, tumbler mixer, etc. After mixing by using, it is melt-kneaded with a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized.

The PP layer resin composition pellets and the SD layer resin composition pellets are charged into an extruder and extruded from a T-die co-extrusion die. The type of T-die may be a multi-manifold type for type 2 and 3 layers or a feed block type for type 2 and 3 layers.
The gap of the T die to be used is determined from the final required film thickness, stretching conditions, draft rate, various conditions, etc., but is generally about 0.1 to 3.0 mm, preferably 0.5. -1.0 mm. If it is less than 0.1 mm, it is not preferable from the viewpoint of production speed, and if it is larger than 3.0 mm, the draft rate is increased, which is not preferable from the viewpoint of production stability.

In extrusion molding, the extrusion processing temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 150 to 300 ° C, and more preferably 180 to 280 ° C. When the temperature is 150 ° C. or higher, the viscosity of the molten resin is preferably sufficiently low and excellent in moldability. On the other hand, at 300 ° C. or lower, the deterioration of the resin composition can be suppressed.
The cooling and solidifying temperature by the cast roll is very important in the present invention, and β crystals in the film-like material before stretching can be generated and grown, and the ratio of β crystals in the film-like material 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.

It is preferable to adjust the β crystal ratio of the obtained film-like material before stretching to 30 to 100% by setting a cast roll in the temperature range. 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 formed by a subsequent stretching operation, and a 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. The crystal melting calorie (ΔHmα) derived from the α crystal and the crystal melting calorie (ΔHmβ) derived from the β crystal are calculated by the following formula.
β crystal ratio (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100

  Next, the obtained laminated nonporous membrane is biaxially stretched. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of producing a laminated porous film excellent in SD characteristics, which is the object of the present invention, sequential biaxial stretching is more preferred because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled. In addition, the extending | stretching to the take-up (flow) direction (MD) of a film-like thing is called "longitudinal stretching", and the extending | stretching to the perpendicular direction (TD) is called "lateral stretching."

  When using sequential biaxial stretching, the stretching temperature needs to be appropriately selected depending on the composition of the resin composition to be used, the crystal melting peak temperature, the crystallinity, etc., but the stretching temperature in the longitudinal stretching is generally 20 ° C. to 130 ° C., It is preferably controlled in the range of 40 ° C to 120 ° C, more preferably 60 ° C 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. The stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10,000% / min, and further preferably 2500 to 8000% / min.

  The laminated porous film thus obtained is preferably heat-treated at a temperature of about 100 ° C. to 170 ° C., preferably about 120 ° C. 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 produced by the production method of the present invention can be applied to various uses requiring 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 warm compresses; ; Building materials such as wallpaper, roof waterproofing material, heat insulating material, sound absorbing material, etc .; desiccant; moisture-proofing agent; oxygen scavenger; disposable body warmer; .

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

In the laminated porous film of the present invention, other physical properties can be freely adjusted by the composition of the resin composition constituting the PP layer and SD layer, the layer structure, the production method, and the like.
For example, when used as a battery separator, the porosity is preferably 5 to 80%, more preferably 20 to 70%, particularly preferably 30 to 70%, and further 40 It is particularly preferred that it is ˜65%. The porosity is an important factor for defining the porous structure. When the porosity is 5% or more, it is possible to obtain a battery separator 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 fine pores are excessively increased and the mechanical strength of the separator is lowered, which is preferable from the viewpoint of handling.

[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. By making the thickness 5 μm or more, the battery separator is difficult to break, and by making the thickness 40 μm or less, it is possible to increase the battery area when wound in a predetermined battery can and thus increase the battery capacity. 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, although an Example and a comparative example are shown and the laminated porous film manufactured with the manufacturing method of this invention is demonstrated still in detail, this invention is not limited to these.
The take-up (flow) direction of the laminated porous film is referred to as a “longitudinal” direction, and the direction perpendicular thereto is referred to as a “lateral” direction.

(Examples 1-8, Comparative Examples 1-3)
Based on the raw material composition of each layer shown in Table 1, each raw material was put into a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (caliber 40 mmφ, L / D = 32) for each layer to produce pellets. Next, the pellets prepared for each layer were put into a 40 mm single screw extruder, extruded from a T-die through a single layer or two-type three-layer feed block according to the layer configuration described in Table 2, and the temperature described in Table 1 The film was taken up with a cast roll and cooled and solidified to obtain a film-like product having a width of 300 mm and a thickness of 200 μm. Next, using a film roll longitudinal stretching machine, the film was stretched in the longitudinal direction between the rolls at the stretching temperature and the stretching ratio listed in Table 1, and then stretched according to Table 1 in a film tenter facility manufactured by Kyoto Machine Co., Ltd. The film was stretched in the transverse direction at a temperature and a draw ratio. Furthermore, thermal relaxation was performed under the conditions described in Table 1 to obtain a laminated porous film.

( Reference Example 9)
Based on the raw material composition of each layer shown in Table 1, each raw material was put into a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (caliber 40 mmφ, L / D = 32) for each layer to produce pellets. Next, the pellets prepared for each layer were put into a 40 mm single screw extruder, the PP layer and the SD layer were each extruded as a single layer, taken up with a cast roll at the temperature shown in Table 1, cooled and solidified, and a width of 300 mm A film having a thickness of 100 μm was obtained.
Then, according to the layer structure described in Table 2, each sheet was laminated at 135 ° C., a nip pressure of 5 kg / cm ² , and a line speed of 5 m / min to obtain a laminated film having a thickness of 200 μm.
Next, using a film roll longitudinal stretching machine, the film was stretched in the longitudinal direction between the rolls at the stretching temperature and the stretching ratio listed in Table 1, and then stretched according to Table 1 in a film tenter facility manufactured by Kyoto Machine Co., Ltd. The film was stretched in the transverse direction at a temperature and a draw ratio. Furthermore, thermal relaxation was performed under the conditions described in Table 1 to obtain a laminated porous film.

( Reference Example 10)
A PP layer similar to that in Example 1 was extruded as a single layer to obtain a film having a thickness of 80 μm.
Thereafter, using a film roll longitudinal stretching machine, after performing uniaxial stretching in the longitudinal direction between the rolls at a stretching temperature of 100 ° C. and a stretching ratio of 4.0 times, the same SD layer as in Example 1 was extruded and laminated. A 35 μm laminated film was obtained.
Next, the film was stretched in the transverse direction at a stretching temperature of 120 ° C. and a stretching ratio of 3.0 times in a film tenter facility manufactured by Kyoto Machine Co. Furthermore, thermal relaxation was performed at a temperature of 125 ° C. and a relaxation rate of 10% to obtain a laminated porous film.

The raw materials used in Examples, Reference 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 Co., Ltd. (MFR 3.0 g / 10 min)
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
N, N′-dicyclohexyl-2,6-naphthalenedicarboxylic acid amide (β1), which is a β crystal nucleating agent, is added to the polypropylene resin (PP-1) at a mass ratio of PP-1 / β1 = 100 / 0.1. Blended and put into a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (caliber 40 mmφ, L / D = 32), melted and mixed at a preset temperature of 280 ° C. Cut to produce a mixed pellet of polypropylene resin (PP-1) and β crystal nucleating agent (β1).
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: “Novatec HD HY530 (trade name)” manufactured by Nippon Polytechnic Co., Ltd.
(MFR 0.55 g / 10 min, Tm 134 ° C., density 0.959 g / cm ³ )
-PE-2: "Hi-Zex 1300J (trade name)" manufactured by Prime Polymer Co., Ltd.
(MFR 12.0 g / 10 min, Tm 134 ° C., density 0.961 g / cm ³ )
(C) Filler FL-1: Barium sulfate “B55 (trade name)” manufactured by Sakai Chemical Co., Ltd. (average particle size 0.66 μm)
FL-2: Barium sulfate “B54 (trade name)” manufactured by Sakai Chemical Industry Co., Ltd. (average particle size 1.2 μm)
(D) Plasticizer / PL-1: “High Castor Wax HCOP (trade name)” manufactured by Toyokuni Seiyaku Co., Ltd.

  About the film of the obtained Example and the comparative example, various characteristics were measured and evaluated as follows, and the result was put together in Table 2.

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

(6) SD characteristics The obtained film was cut into a 60 mm × 60 mm square, and as shown in FIG. 2 (A), an aluminum plate (material: JIS standard A5052, Size: 60 mm long, 60 mm wide, 1 mm thick) sandwiched between two sheets and restrained by a clip (made by KOKYO Corporation, double clip “Kuri-J35 (trade name)”) as shown in FIG. 2 (B) .
Put the film restrained by two aluminum plates into an oven set at 100 ° C or 150 ° C (Tabai Espec, Tabai Gear Oven "GPH200 (trade name)", damper closed state) After the temperature rose to each temperature, it was held for 3 minutes, and then immediately removed and cooled in an atmosphere of 25 ° C. for 30 minutes 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. The sample was heated and taken out after 3 minutes, and the air resistance was measured according to JIS P8117.
The case where the air resistance after heating was 10 times or more of the air resistance before heating was marked with ●, and the case where it was less than 10 times was marked with ○.
The preferred shutdown temperature range in the present invention is more than 100 ° C. and not more than 150 ° C., so in this evaluation, the air resistance is not reduced at 100 ° C., and at 150 ° C., the air resistance is reduced by shutdown. ● is preferred.
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.

(7) BD characteristics An oven (Tabaye Gear Oven, GPH200 (product of Tabay Espec, Inc.) in which a film fixed to two aluminum plates in the same manner as FIGS. 2 (A) and 2 (B) is set at 180 ° C. Name) ”, the damper closed state), and after 2 minutes after the oven set temperature reached 180 ° C. again, the film was taken out and the state of the film was confirmed to determine the shape maintenance performance.
When the film was broken, it was evaluated as “X”, and when the shape was maintained, it was evaluated as “◯”.

(8) Thermal shrinkage A 50 mm square film was prepared, and the dimension (L0) before heating was accurately measured. The film was taken out after being left in an oven set at 105 ° C. (Tabai Espec, Tabai Gear Oven “GPH200 (trade name)”) for 1 hour, and the dimension (L1) after heating was measured, and the vertical and horizontal directions were measured. The shrinkage in each direction was determined from the following formula. When it is extended by heating, it is minus.
Thermal contraction rate = {(L0−L1) / L0} × 100

  Further, the obtained film was evaluated for β activity and β crystal forming power as follows, and the results are summarized in Table 3.

(9) β activity The film was heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min for 1 minute using a differential scanning calorimeter (DSC-7) manufactured by Perkin Elmer Co. 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.

(10) β Crystal Forming Power As in the case of the measurement of the SD characteristic, the film was cut into a 60 mm long × 60 mm wide square and fixed as shown in FIGS. 2 (A) and 2 (B).
The film in a state of being restrained by two aluminum plates is placed in a ventilation constant temperature thermostat (model DKN602, manufactured by Yamato Kagaku Co., Ltd.) having a set temperature of 180 ° C. and a display temperature of 180 ° C., and held for 3 minutes. The temperature was changed and gradually cooled to 100 ° C. over 10 minutes. When the display temperature reaches 100 ° C., the film is taken out and cooled in an atmosphere of 25 ° C. for 5 minutes while being restrained by two aluminum plates. Wide-angle X-ray measurement was performed on a 40 mmφ circular portion.
-Wide-angle X-ray measuring device: manufactured by Mac Science Co., Ltd. Model No. XMP18A
X-ray source: CuKα ray, output: 40 kV, 200 mA
Scanning method: 2θ / θ scan, 2θ range: 5 ° to 25 °, scanning interval: 0.05 °, scanning speed: 5 ° / min
About the obtained diffraction profile, the presence or absence of the β crystal generation force was evaluated from the peak derived from the (300) plane of the β crystal of polypropylene as follows.
◯: When a peak is detected in the range of 2θ = 16.0 to 16.5 ° (with β-crystal forming power)
X: When a peak is 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.

As is apparent from Tables 2 and 3, Comparative Example 1 consisting only of a PP layer having β activity and β crystal generation power does not have SD characteristics, and conversely, it consists only of an SD layer, and β activity and β crystal generation power. Comparative Example 2 having no BD did not have BD characteristics.
Moreover, in the comparative example 3 which does not have (beta) activity and (beta) crystal formation power using the polypropylene-type resin which does not have (beta) activity, it fractured | ruptured during extending | stretching and the laminated porous film was not able to be produced.
On the other hand, it was found that the laminated porous film of the present invention has air permeability resistance suitable as a battery separator and has both SD characteristics and BD characteristics.

  The laminated porous film of the present invention can be suitably used as a battery separator because of its excellent property of having both the SD function and the BD function.

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

Claims (5)

a layer (PP layer) made of a polypropylene resin containing a β crystal nucleating agent and having β activity and / or β crystal generation ability;
A peak value of the crystal melting temperature is lower than that of the polypropylene-based resin, and a thermoplastic resin composition containing a thermoplastic resin and a barium sulfate having a crystal melting peak temperature of 100 ° C. or higher and 150 ° C. or lower is used. in Ri Do of at least two layers of the layer to shut down (SD layer), the shutdown temperature of the hole of the SD layer is closed will produce a laminated unporous membrane material is less than 0.99 ° C. exceed 100 ° C.,
A method of making the SD layer porous is a filler method,
A method for producing a laminated porous film, characterized in that a number of micropores having communication in the thickness direction are formed by biaxially stretching the laminated nonporous film-like material.   The method for producing a laminated porous film according to claim 1, wherein the laminated nonporous film-like material is produced by coextrusion.   The manufacturing method of the laminated porous film of Claim 1 or Claim 2 which laminated | stacked said PP layer and said SD layer by 2 types and 3 layers at the process of coextrusion. The method for producing a laminated porous film according to any one of claims 1 to 3 , wherein the thermoplastic resin having a crystal melting peak temperature of 100 ° C or higher and 150 ° C or lower is a polyethylene resin. The laminated porous body according to any one of claims 1 to 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. For producing a conductive film.

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