JP6194938B2 - Laminated porous stretched film, battery separator and battery using the same - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention can be used as a packaging product, sanitary product, livestock product, agricultural product, building product, medical product, separation membrane, light diffusion plate, battery separator, and particularly a laminate that can be suitably used as a nonaqueous electrolyte battery separator. The present invention relates to a porous stretched film , a battery separator using the same, and a battery .

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

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

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

With the recent increase in battery capacity, the importance of battery safety has increased.
A characteristic that contributes to the safety of battery separators is breakdown characteristics (hereinafter referred to as BD characteristics). This BD characteristic is a function that the film does not break and keeps the positive electrode and the negative electrode separated even when the battery becomes abnormal and the thermal runaway causes a high temperature of about 160 ° C. or more. 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 it is used as a battery separator, it preferably has this BD characteristic, and the breakdown temperature indicating the lowest temperature at which film breakage occurs is preferably a higher temperature.

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.
The separator manufactured by the manufacturing method has heat resistance because a polypropylene layer having a higher crystal melting peak temperature than that of a conventional polyethylene single layer separator is laminated, and is advantageous from the viewpoint of BD characteristics. However, with the recent increase in energy density of batteries, it is difficult to say that heat resistance is sufficient for polypropylene, and it is required that BD characteristics can be exhibited even at higher temperatures.
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 in terms of strength that a tear is easily generated in the stretching direction.
In addition, the manufacturing method requires strict control of manufacturing conditions, and it is difficult to say that productivity is good.

On the other hand, as a method for obtaining a porous film by stretching a polypropylene sheet containing a large amount of β crystals, which is one of crystal forms, in order to increase the permeability of the porous film, Japanese Patent No. 2509030 (Patent Document 2), International Publication 2002/066233 (Patent Document 3) has been proposed.
However, the heat resistance is not sufficient to use any porous film as a battery separator, and there is a problem in securing the safety of the battery, and the breakdown temperature is improved to be higher. It is requested to do.

Japanese Patent No. 2883726 Japanese Patent No. 2509030 International Publication No. 2002/066233 Pamphlet

The present invention relates to a laminated porous stretched film having excellent air permeability and mechanical strength and capable of exhibiting a breakdown characteristic superior to that of a conventional polypropylene porous film , a battery separator and a battery using the same. The challenge is to propose.

To solve the above problems, the present invention is a laminated porous expanded fill beam having a porous layer of at least first and second layers,
The first layer, the polypropylene-based resin, Ri layer der ing a resin composition crystal melting peak temperature is mixed with the thermoplastic resin is 170 ° C. or higher,
The second layer is composed of a resin composition in which a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher is not mixed with a polypropylene resin blended with a β crystal nucleating agent, and has β activity and / or β crystal. A layer having a generating power ,
An air resistance is 1-10000 seconds / 100 ml, the pin stab strength of not less than 1.5 N, the breakdown temperature of 200 ° C. or higher, that provides a laminated porous film.
Moreover, the battery separator which consists of the said laminated porous stretched film and whose air permeation resistance is 5-3000 second / ml, and the battery separator are incorporated are provided.

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Product layer porous stretched film of the present invention, since the first layer is formed from a resin composition crystal melting peak temperature and the polypropylene resin comprises a mixed resin of the thermoplastic resin is 170 ° C. or higher, heat resistance It is possible to exhibit a breakdown characteristic superior to that of a conventional polypropylene porous film. In addition, the second layer can be made a layer having excellent mechanical strength by increasing the amount of polypropylene resin without blending the thermoplastic resin with polypropylene resin. Thus, the laminated porous stretched film of the present invention can have excellent mechanical strength and breakdown characteristics, and when the laminated porous stretched film of the present invention is used for a battery separator, Contributes greatly to ensuring battery safety.
Furthermore, since the laminated porous stretched film of the present invention has β activity and / or β crystal generation ability, it has fine pores, can ensure sufficient communication, and has excellent air permeability. .
Also, when winding the electrode and separator in battery manufacturing, or when the electrode repeatedly expands and contracts during charge and discharge, the separator breaks due to electrode irregularities and burrs, causing a short circuit between the two electrodes. It can be hard to happen.

It is a partially broken perspective view of the nonaqueous electrolyte battery which accommodates the lamination | stacking porous stretched film of this invention as a battery separator. (A) (B) is a figure explaining the restraint method of the film in the measurement of breakdown temperature and (beta) crystal formation power.

Hereinafter, embodiments of the product layer porous stretched film of the present invention, as well as the adaptations to the battery as a battery separator will be described in detail.
Product layer porous stretched film of the present invention, in any embodiment, is configured to include a porous layer of at least two layers of a first layer porous layer and a porous layer of the second layer of.

[First Embodiment]
The laminated porous film of the first embodiment includes a polypropylene resin (hereinafter referred to as “PP resin”) containing a β crystal nucleating agent and a thermoplastic resin (hereinafter referred to as “HM resin”) having a crystal melting peak temperature of 170 ° C. or higher. A thermoplastic resin (HM resin) having a crystal melting peak temperature of 170 ° C. or higher, and a polypropylene resin containing a first layer formed from a composition containing a mixed resin and a β crystal nucleating agent And a second layer having a crystal melting peak temperature of 100 ° C. or higher and lower than 170 ° C.
In particular, the first layer is a layer that exhibits breakdown characteristics, and the second layer is a layer that imparts mechanical strength.

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

Presence or absence of the β activity is determined by performing differential thermal analysis of the laminated porous film using a differential scanning calorimeter and determining whether or not a crystal melting peak temperature derived from β crystals of the polypropylene resin is detected. doing.
Specifically, the laminated porous film is heated at a heating rate of 10 ° C./min from 25 ° C. to 240 ° C. for 1 minute with a differential scanning calorimeter, and then cooled from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C. / When the temperature is lowered for 1 minute and held for 1 minute, and when the temperature is raised again from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min, the crystal melting peak temperature (Tmβ) derived from the β crystal of the polypropylene resin is detected. In that case, it is determined to have β activity.

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

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

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

As a method for obtaining the β activity and / or β crystal generation power of the porous layer described above, as described in a method in which a substance that promotes the formation of α crystal of a polypropylene resin is not added, or as described in Japanese Patent No. 3739481 The method of adding the polypropylene which performed the process which generates a peroxide radical, the method of adding a (beta) crystal nucleating agent to a composition, etc. are mentioned.
In the present invention, a β crystal nucleating agent is added to the composition of the first layer and / or the composition of the second layer to obtain β activity and / or β crystal generation power. By adding a β crystal nucleating agent, it is possible to promote the generation of β crystals of polypropylene resin more uniformly and efficiently, and to obtain a laminated porous film having β activity and / or β crystal generation ability. it can.

In the present invention, the β crystal nucleating agent is blended in a polypropylene resin. The ratio of the β-crystal nucleating agent added to the polypropylene resin needs to be appropriately adjusted depending on the type of the β-crystal nucleating agent or the composition of the polypropylene-based resin. 0.0001 to 5.0 parts by mass of the agent is preferred. 0.001-3.0 mass parts is more preferable, and 0.01-1.0 mass part is still more preferable. If it is 0.0001 part by mass or more, β-crystals of polypropylene resin can be sufficiently produced and grown during production, and sufficient β-activity and / or β-crystal-forming power can be secured even when used as a separator. Desired air permeation performance can be obtained. The addition of 5.0 parts by mass or less is preferable because it is economically advantageous and there is no β crystal nucleating agent on the surface of the laminated porous film.
In the present invention, the addition amount of the β crystal nucleating agent may be the same or different between the first layer and the second layer. The porous structure of each layer can be appropriately adjusted by changing the addition amount of the β crystal nucleating agent.

In the first layer, the total mass of the PP resin and the HM resin is preferably 70% by mass or more based on the total mass of the first layer. Preferably it accounts for 80% by mass or more, more preferably 90% by mass or more.
The mixing mass ratio of PP resin and HM resin is preferably PP resin / HM resin = 10 to 90/90 to 10, more preferably 20 to 80/80 to 20, and 30 to 70/70 to 30. Further preferred. When the content of the HM resin is 10% by mass or more in the total mass of 100% by mass of the PP resin and the HM resin, it is possible to develop the BD characteristics at an appropriate temperature. On the other hand, when the content of the HM resin is 90% by mass or less in the total mass of 100% by mass of the PP resin and the HM resin, the first layer is easily made porous, which is preferable.
Of these, a higher PP resin content is preferred, with PP resin / HM resin = 60-90 / 40-10 being more preferred, and 60-70 / 40-30 being even more preferred.

When the laminated porous film has three or more layers and the plurality of first layers are present, the mixing mass ratio of the PP resin and the HM resin in one first layer is within the specified range.
The mixing mass ratio of PP resin and HM resin in the other layers is preferably PP resin / HM resin = 10 to 99/90 to 1, more preferably 30 to 99/70 to 1, and 60 to 99. / 40-1 is more preferable, and 60-90 / 40-10 is particularly preferable.
Since it is sufficient that at least one layer that exhibits the BD characteristic exists, the BD characteristic is not necessarily required for the other first layers. Therefore, about 1st mass other than that, content of HM resin should just be 1 mass% or more in 100 mass% of total mass of PP resin and HM resin. Of course, there is no problem even if all of the first layer develops the BD characteristic, but it is preferable. On the other hand, when the content of the HM resin is 90% by mass or less in the total mass of 100% by mass of the PP resin and the HM resin, the first layer is easily made porous, which is preferable.

  In the second layer, the content of the PP resin is preferably 70% by mass or more based on the total mass of the second layer. More preferably, it is configured to occupy 80% by mass or more, and most preferably 90% by mass or more. In addition, in order to improve mechanical strength, you may combine another thermoplastic resin with PP resin.

Below, each component which comprises the laminated porous film of this invention is demonstrated.
[Description of polypropylene resin (PP resin)]
Examples of polypropylene resins include homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Examples thereof include random copolymers with α-olefins and block copolymers. Among these, homopolypropylene is more preferably used from the viewpoint of the mechanical strength of the laminated porous film.

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

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

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

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

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

Among these, as the amide compound represented by the general formula (I), (II), or (III), an amide compound represented by the following general formula (1), (2), or (3) is particularly preferable. It is mentioned as one aspect | mode of an agent.
The amide compound represented by the general formula (1) included in the general formula (I) is:
R ₂ —NHCO—R ₁ —CONH—R ₃ (1)
(In the formula, R ₁ represents a saturated or unsaturated aliphatic, alicyclic or aromatic dicarboxylic acid residue having ₁ to 28 carbon atoms;
R ₂ and R ₃ may be the same or different, and a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group,
The following formula (a);

Following formula (b);

Following formula (c);

Or the following formula (d);

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

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.

The amide compound represented by the general formula (3) contained in the general formula (III) is
R ₁₅ —CONH—R ₁₆ —NHCO—R ₁₇ (3)
(In the formula, R ₁₅ represents an aliphatic diamine residue having 1 to 24 carbon atoms, an alicyclic diamine residue or an aromatic diamino acid residue;
R ₁₆ and R ₁₇ may be the same or different and each is a C 3-12 cycloalkenyl group, cycloalkyl group,
Following formula (i);

Following formula (j);

Following formula (k);

Or the following formula (l);

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

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

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

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

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

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

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

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 dihydroquinacridone type compounds such as dibenzodihydroquinacridone.

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, metal from group IIa of the periodic table and formula (5);

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

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

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.

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.

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.

The cyclic phosphorus compound represented by the general formula (9) is

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Description of Thermoplastic Resin (HM Resin) with Crystal Melting Peak Temperature of 170 ° C. or More]
It is important that the thermoplastic resin (HM resin) having a crystal melting peak temperature of 170 ° C. or higher has a crystal melting peak temperature of 170 ° C. or higher, and the thermoplastic resin is contained in the first layer. The laminated porous film can be provided with excellent heat resistance and can exhibit excellent breakdown characteristics. The upper limit of the crystal melting peak temperature of the thermoplastic resin (HM resin) is not particularly limited, but if it is 350 ° C. or lower, the deterioration of the resin during molding is suppressed, and the resulting laminated porous film machine It is preferable because the mechanical strength can be maintained. The upper limit is more preferably 300 ° C. or lower.
Here H M resin, in compliance with JIS K7121, using a differential scanning calorimeter, when the temperature was raised at a heating rate 10 ° C. / min to 25 ° C. to 400 ° C., the crystalline melting temperature detected A resin having a peak value of 170 ° C. or higher is shown.

H The M resin, with the polypropylene resin (PP resin) is different from the resin, and is not particularly limited as long as it satisfies the requirement of the crystal melting peak temperature. Moreover, you may use the mixture of 2 or more types of resin as needed.
Specifically, for example, polyolefin resins such as polymethyl pentene; polyacetals, Po Riete ether ketone, polyether resins such as also properly polyphenylene sulfide; 6 nylon, 6-6 nylon or 6-12 polyamides such as nylon system resin; polystyrene resins; Po polyvinyl chloride resin; fluorine resin; polyester resins; heat-resistant thermoplastic resin aramid resins.
These may be used alone or in combination of two or more.
Among these, one or more resins selected from the group consisting of polyester resins, polystyrene resins, fluorine resins, and polymethylpentene can be suitably used.
From the viewpoint of compatibility with the polypropylene resin to be mixed, polymethylpentene is particularly preferable.

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

Examples of the polystyrene-based resin include homopolymers of styrene. More specifically, examples include atactic polystyrene and syndiotactic polystyrene.
Among these, syndiotactic polystyrene with high crystallinity is more preferably used from the viewpoint of improving the heat resistance of the lithium ion battery separator of the present invention.
The polystyrene resin can be produced by a known method, or a commercially available product may be used. For example, as syndiotactic polystyrene, the trade name “Zarek” (manufactured by Idemitsu Kosan Co., Ltd.) is available as a commercial product.

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

  The viscosity at the time of melting of the HM resin is not particularly limited, but in order to improve the dispersion state with the PP resin at the time of molding and to make a laminated porous film with higher uniformity and homogeneity, It is preferable to select one having a viscosity similar to that of PP resin. The melt viscosity can generally be adjusted by the molecular weight of the resin.

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

  If necessary, the first layer and the second layer may be added with what is called a rubber component such as a thermoplastic elastomer within a range that does not impair the heat resistance characteristics of the laminated porous film, specifically, the BD characteristics. You may do it. Examples of the thermoplastic elastomer include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.

[Description of composition of laminated porous film]
The configuration of the laminated porous film of the first embodiment is not particularly limited as long as at least the first layer and the second layer, which are basic configurations, are present. As long as the function of the laminated porous film of the present invention is not hindered, other layers may be laminated, or a known treatment may be appropriately performed.
The simplest structure is a two-layer structure laminated with a first layer / second layer.
Next, a simple structure is a three-layer structure in which a first layer / second layer / first layer and a second layer / first layer / second layer are stacked. In the case of the former configuration, the content of the HM resin in the two first layers may be the same or different.
In addition, it is possible to adopt a form of three types and three layers in combination with layers having other functions. In this case, the stacking order of the first layer, the second layer, and the layer having other functions is not particularly limited.
Further, the number of layers may be increased as necessary to 4 layers, 5 layers, 6 layers, and 7 layers. When there are two or more first layers, the content of the HM resin in each first layer may be the same or different.
One particularly preferred embodiment is a three-layer configuration of second layer / first layer / second layer. By adopting this three-layer structure, a laminated porous film having excellent air permeability characteristics and mechanical strength and having BD characteristics can be obtained with higher productivity and economy.

  Regarding the stacking ratio between the first layer and the second layer, the value of the second layer (the total thickness when there are two or more layers) / the first layer (the total thickness when there are two or more layers) is 0. It is 1-10, Preferably it is 0.3-5, More preferably, it is 0.5-3. If it is less than 0.1, the mechanical strength may not be sufficiently exhibited because the second layer is substantially absent. On the other hand, when the ratio is larger than 10, it is difficult to ensure the safety of the battery from the viewpoint that the BD characteristics are insufficient. Moreover, when other layers other than a 1st layer and a 2nd layer exist, the sum total of the thickness of the said other layer is 0.1-0.5 with respect to the whole thickness 1, Preferably it is 0.1-0 .3.

[Description of shape and physical properties of laminated porous film]
The form of the laminated porous film of the first embodiment may be either a flat shape or a tube shape. However, it is possible to take several products as products in the width direction, and the productivity is good, and the inner surface is coated. The planar shape is more preferable from the viewpoint of being capable of processing such as.
The thickness of the laminated porous film of the present invention is 1 to 500 μm, preferably 5 to 300 μm, and more preferably 7 to 100 μm. When using as a battery separator especially, 1-50 micrometers is preferable and 10-30 micrometers is more preferable. When used as a battery separator, if the thickness is 1 μm or more, preferably 10 μm or more, substantially necessary electrical insulation can be obtained. For example, even when a large voltage is applied, it is difficult to short-circuit and is safe. Excellent. Further, if the thickness is 50 μm or less, preferably 30 μm or less, the electric resistance of the laminated porous film can be reduced, so that the battery performance can be sufficiently secured.

The physical properties of the laminated porous film of the present invention can be freely adjusted by the layer constitution, the lamination ratio, the composition of each layer, and the production method.
The laminated porous film of the present invention preferably exhibits BD characteristics at 200 ° C. or higher. That is, the breakdown temperature of the laminated porous film of the present invention is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 240 ° C. or higher. If the breakdown temperature is 200 ° C. or higher, for example, when the laminated porous film of the present invention is incorporated into a battery as a battery separator, the battery also stores or generates heat and the battery separator is exposed to a high temperature. The battery separator does not break, and is excellent in safety as a battery. On the other hand, the upper limit of the breakdown temperature is not particularly limited, but is about 400 ° C. due to the processing temperature of raw materials.
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.
The breakdown temperature can be adjusted by increasing the mass ratio of the HM resin, increasing the layer ratio of the first layer, or the like.

The air-permeable resistance of the laminated porous film of the present invention is 1 to 10,000 seconds / 100 ml, preferably 5 to 3000 seconds / 100 ml, and more preferably 10 to 2000 seconds / 100 ml. If the air resistance is greater than 10,000 seconds / 100 ml, the numerical value of the air resistance will be obtained in the measurement, but it means that the structure is quite poor in communication, so there may be substantially no communication. Many.
The air permeation resistance represents the difficulty of air passage in the film thickness direction, and is specifically expressed in the number of seconds required for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means poor communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction. If the air permeability resistance of the laminated porous film of the present invention is low, it can be used for various applications. For example, when used as a separator of a lithium ion secondary battery, a low air permeability resistance means that lithium ions can be easily transferred, which is preferable because the battery performance is excellent.

In the laminated porous film of the present invention, the porosity is preferably 5 to 80%, more preferably 20 to 70%. The porosity is an important factor for defining the porous structure. When the porosity is 5% or more, it is possible to obtain a laminated porous film that ensures communication and has excellent air permeability. On the other hand, if the porosity is 80% or less, there is no problem that the fine pores increase and the mechanical strength of the film decreases, which is preferable from the viewpoint of handling.
For example, as a means for increasing the porosity, there is a means for increasing the mass ratio of the HM resin in the first layer, and a means for setting the stretching temperature to a lower temperature within the range defined by the present invention is effective. .
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.
The pin puncture strength is a value of breaking strength when a needle is pierced into the surface of the laminated porous film, and is a value serving as an index of mechanical strength of the film. Specifically, it is measured by the method described in the examples.
Pin puncture strength greatly contributes to short-circuiting and productivity during battery production, particularly when the laminated porous film of the present invention is used as a battery separator. If the pin piercing strength is lower than 1.5N, the film is easily broken when contacting the metal edge or protrusion during battery production, and as a result, the probability of occurrence of a short circuit due to direct contact between the positive electrode and the negative electrode increases.
On the other hand, the upper limit value of the pin puncture strength is not particularly defined, but a value of 10 N or less is usually used from the viewpoint of handling.

Moreover, in the laminated porous film of this invention, it is preferable that the anisotropy is small from a viewpoint of film physical property. As an anisotropy index, it can be expressed by 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.

[Description of Method for Producing Laminated Porous Film]
Next, the manufacturing method of the laminated porous film of this invention is demonstrated.
The manufacturing method of the laminated porous film of this invention is divided roughly into the following two by the order of porous formation and lamination.
(A) A method of laminating each porous layer after laminating each porous layer or bonding with an adhesive or the like. (Production method of the second invention corresponding to claim 3)
(B) A method of laminating each layer to produce a laminated nonporous film-like material and then making the nonporous film-like material porous. (Production method of the first invention corresponding to claim 1)
In the present invention, it is preferable to use the method (b) from the viewpoint of simplification of the process and productivity, and in particular, in order to ensure the interlayer adhesion between the two layers, a directly laminated nonporous film-like material is formed by coextrusion. A method of forming a porous layer after production is particularly preferred.

In the manufacturing method of the first invention, specifically, the thermoplastic resin composition for the first layer containing PP resin and HM resin, and the thermoplastic for the second layer containing PP resin and no HM resin. Using the resin composition, a laminated non-porous film-like material composed of at least two layers of a first layer and a second layer is produced by coextrusion, and the laminated non-porous film-like material is stretched to communicate in the thickness direction. A large number of micropores having the above are formed.
Moreover, also in the said manufacturing method, in order to ensure the interlayer adhesiveness in coextrusion, it is preferable that the ratio of PP resin of each layer is 50 mass% or more.

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

Below, the detail of the manufacturing method of the lamination | stacking porous film of 1st Embodiment is demonstrated. The manufacturing method of the laminated porous film of the second embodiment to be described later is exactly the same except that the components of the second layer are different.
First, a thermoplastic resin composition containing PP resin and HM resin that will constitute the first layer is prepared.
For example, raw materials such as polypropylene resin, β crystal nucleating agent, HM resin and other additives as required, preferably using a Henschel mixer, a super mixer, a tumbler type mixer, etc., or putting all ingredients in a bag After mixing by hand blending, 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 to obtain pellets of the resin composition for the first layer.

Next, a thermoplastic resin composition that includes the PP resin that will form the second layer and does not include the HM resin is prepared.
For example, raw materials such as polypropylene resin, β crystal nucleating agent and other additives as required, preferably by using a Henschel mixer, a super mixer, a tumbler type mixer, etc. Are mixed and then melt-kneaded with a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized to obtain pellets of the resin composition for the second layer.

The pellets of the resin composition for the first layer and the pellets of the resin composition for the second layer are put into separate extruders and extruded from a die for T-die coextrusion to form a film. The type of T die is not particularly limited. For example, when the laminated porous film of the present invention has a two-kind three-layer structure, the T die may be a two-kind three-layer multi-manifold type or a two-kind three-layer feed block type.
The gap of the T die to be used is determined from the final required film thickness, stretching conditions, draft rate, various conditions, etc., but is generally about 0.1 to 3.0 mm, preferably 0.5. -1.0 mm. If it is less than 0.1 mm, it is not preferable from the viewpoint of production speed, and if it is more than 3.0 mm, it is not preferable from the viewpoint of production stability because the draft rate increases.

In extrusion molding, the extrusion temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 180 to 350 ° C, more preferably 200 to 330 ° C, and still more preferably 220 to 310 ° C. A temperature of 180 ° C. or higher is preferable because the viscosity of the molten resin is sufficiently low and the moldability is excellent and the productivity is improved. On the other hand, by setting the temperature to 350 ° C. or lower, it is possible to suppress the deterioration of the resin composition, and hence the mechanical strength of the resulting laminated porous film.
The cooling and solidification temperature by the cast roll is very important in the present invention, and β crystal of PP resin can be generated and grown, and the ratio of β crystal of PP resin in the film can be adjusted. The cooling and solidification temperature of the cast roll is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, and still more preferably 100 to 130 ° C. By setting the cooling and solidifying temperature to 80 ° C. or higher, the ratio of β crystals in the cooled and solidified film can be sufficiently increased, which is preferable. Further, it is preferable to set the temperature to 150 ° C. or lower because troubles such as the extruded molten resin sticking to and wrapping around the cast roll hardly occur and the film can be efficiently formed into a film.

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

  Next, the obtained laminated nonporous membrane is biaxially stretched. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. Among these, sequential biaxial stretching is more preferable because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled. In addition, extending | stretching to the take-up (flow) direction of a film-form thing is called "longitudinal stretching" (MD), and extending | stretching to the orthogonal | vertical direction is called "lateral stretching" (TD).

When sequential biaxial stretching is used, the stretching temperature needs to be appropriately selected depending on the composition of the resin composition used, the crystal melting peak temperature of the HM resin, the crystallinity of the PP resin, etc., but is selected within the range of the following conditions. It is preferable.
The stretching temperature in the longitudinal stretching is generally controlled in the range of 20 ° C to 130 ° C, preferably 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 3 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.
A stretching temperature in the longitudinal stretching of 20 ° C. or higher is preferable because breakage during stretching is suppressed and uniform stretching is performed. On the other hand, if the stretching temperature in the longitudinal stretching is 130 ° C. or lower, two types of hole formation, namely, hole formation in the PP resin and hole formation by interfacial separation between the PP resin and the HM resin occur. Hole formation can be performed. Further, the pores formed in this way are not easily blocked by the subsequent transverse stretching, and can exhibit air permeability characteristics even when the transverse stretching temperature is raised, for example, which is very useful in production. If the stretching temperature in the longitudinal stretching is set to 110 ° C. or less, the effect becomes more prominent.

On the other hand, the stretching temperature in transverse stretching is generally 100 ° C to 160 ° C, preferably 110 ° C to 150 ° C, more preferably 120 ° C to 140 ° C. The transverse draw ratio is preferably 2 to 10 times, more preferably 3 to 8 times, and further preferably 4 to 7 times. By transversely stretching within the above range, the pore starting point formed by longitudinal stretching can be appropriately expanded and a fine porous structure can be expressed, and as a result, a laminated porous film having excellent air permeability characteristics. Can be obtained.
In particular, if the longitudinal stretching is performed at a relatively low temperature as described above, the pores are less likely to be clogged. Therefore, the stretching temperature in the lateral stretching is superior to the stretchability and the productivity is improved when the stretching temperature is 120 ° C. It is preferable from the point.

In the present invention, the stretching temperature (T _TD ) and the longitudinal length in transverse (TD) stretching are used to control the porosity in the stretching step and to exhibit excellent air permeability properties by forming an ideal porous structure. (MD) the difference between the stretching temperature _{(T MD)} in the stretching is _preferably T TD _{-T MD} is 30 ° C. to 60 ° C., and more preferably 40 ° C. to 55 ° C..

  The stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10,000% / min, and further preferably 2500 to 8000% / min. When the stretching speed is in this range, the laminated porous film of the present invention can be produced efficiently.

  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 150 ° 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 that require air permeability. Battery separators; Sanitary materials such as disposable paper diapers and sanitary items such as pads and bed sheets for absorbing body fluids; Medical materials such as surgical clothing or base materials for hot compresses; Materials for clothing such as jumpers, sportswear, and rainwear ; Building materials such as wallpaper, roof waterproofing material, heat insulating material, sound absorbing material; desiccant; moisture-proofing agent; oxygen scavenger; disposable body warmer; can be used very suitably as a material for packaging materials such as freshness preservation packaging or food packaging .

[Description of Reference Second Embodiment]
The reference second embodiment is different from the first embodiment in that the second layer is also a mixed resin of PP resin and HM resin, and the blending ratio of the HM resin is smaller than that of the first layer. That is, in the reference second embodiment, a plurality of layers containing a mixed resin of PP resin and HM resin are provided, and the blending ratio of HM resin in these layers is made different.

Specifically, the content (mass%) of the HM resin in the layer having the highest content of HM resin (first layer) and the content of the HM resin in the layer having the lowest content of HM resin (second layer). The difference from the rate (% by mass) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass.
The mixed mass ratio of the PP resin and the HM resin in the layers other than the first layer and the second layer is preferably PP resin / HM resin = 10 to 99/90 to 1, and 30 to 99/70 to 1 Is more preferable, 60 to 99/40 to 1 is still more preferable, and 60 to 90/40 to 10 is particularly preferable.
Since it is sufficient that at least one layer of the first layer is present in the BD characteristic, the BD characteristic is not necessarily required for the other layers. Therefore, the content of the HM resin may be 1% by mass or more in 100% by mass of the total mass of the PP resin and the HM resin. On the other hand, if the content of the HM resin exceeds 90% by mass in 100% by mass of the total mass of the PP resin and the HM resin, it becomes difficult to make the material porous.
Since other components and configurations are the same as those in the first embodiment, description thereof is omitted.

The laminated porous film of the first embodiment is suitably used as a separator for a non-aqueous electrolyte battery such as a lithium ion secondary battery used as a power source for various electronic devices.
When used as the battery separator, the air permeability resistance is preferably 5 to 3000 seconds / 100 ml, more preferably 20 to 2000 seconds / 100 ml, still more preferably 50 to 1000 seconds / 100 ml, Most preferably, it is 50 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. There is often no degree of connectivity. That is, it is preferable that the air permeation resistance is 3000 seconds / 100 ml or less because ion conductivity can be secured and sufficient battery characteristics can be obtained. On the other hand, if the air permeation resistance is 5 seconds / 100 ml or more, it is preferable because the pore diameter is appropriately small and the mechanical strength of the laminated porous film can be maintained.
The air permeation resistance represents the difficulty of air passing through in the thickness direction of the separator, and is specifically expressed by the number of seconds required for 100 ml of air to pass through the separator. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means that the separator in the thickness direction is better, and a larger value means that the separator is less in the thickness direction. Communicability is the degree of connection of holes in the thickness direction of the separator. The low air permeability resistance of the lithium ion battery separator of the present invention means that lithium ions can be easily transferred, which is preferable because of excellent battery performance.

  When the laminated porous film of the present invention is used as a battery separator, the porosity is preferably 30 to 70%, more preferably 40 to 65%. If the porosity is 30% or more, ion permeability can be ensured and sufficient battery performance can be obtained. On the other hand, from the viewpoint of battery safety, the porosity is preferably 70% or less.

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

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

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

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

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

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

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

[Description of Examples]
The following Comparative Example and Contact embodiment, will be described in more detail the laminated porous film of the present invention, but the present invention is not limited thereto.
The take-up (flow) direction of the laminated porous film is referred to as a “longitudinal” direction, and the direction perpendicular thereto is referred to as a “lateral” direction.

(Example, the ratio Comparative Examples)
As shown in Table 1, each raw material of the first layer was transferred to the same direction twin screw extruder (caliber: 30 mmφ, L / D = 30) manufactured by Technobel, and each raw material of the second layer was manufactured by Toshiba Machine Co., Ltd. Into the same direction twin screw extruder (caliber 40 mmφ, L / D = 32), melt and mix at 290 ° C., then, depending on the layer structure described in Table 1, single layer, two types or two layers It was extruded from a T-die through a feed block, taken up with a cast roll having the temperature shown in Table 1, and cooled and solidified to obtain an unstretched film having a width of 300 mm and a thickness of 180 μm. At this time, the (cooling) contact time between the molten resin film and the cast roll was 12 seconds.
Next, the obtained unstretched film-like material was stretched in the longitudinal direction at a stretching temperature and a stretching ratio shown in Table 1 between rolls using a film roll longitudinal stretching machine, and then a film manufactured by Kyoto Machine Co., Ltd. In a tenter facility, the film was stretched in the transverse direction at the stretching temperature and stretch ratio shown in Table 1. Furthermore, thermal relaxation was performed under the conditions described in Table 1 to obtain a laminated porous film.

Example, raw materials were used in the ratio Comparative Examples are as follows.
In addition, about each polypropylene-type resin (PP-1, (beta) PP-1, (beta) PP-2), the heating rate 10 from 25 degreeC to 240 degreeC using the differential scanning calorimeter (DSC-7) by Perkin-Elmer Co., Ltd. Hold at 1 ° C./min and hold for 1 minute, then cool down from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C./min and hold for 1 min. Whether or not a crystal melting peak (Tmβ) derived from the β crystal is detected in the range of 145 ° C. or more and less than 160 ° C. when the temperature is 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
After adding 0.1 part by mass of N, N′-dicyclohexyl-2,6-naphthalenedicarboxylic acid amide, which is a β crystal nucleating agent, to 100 parts by mass of the polypropylene resin (PP-1), hand blending is performed. Put into a twin screw extruder manufactured by Co., Ltd. (caliber 40 mmφ, L / D = 32), melt and mix at a set temperature of 280 ° C., cool and solidify the strand in a water bath, cut the strand with a pelletizer, and polypropylene A mixed pellet of resin (PP-1) and β crystal nucleating agent was prepared.
At the time of reheating, a crystal melting peak temperature (Tmβ) derived from polypropylene β crystal was detected at 154 ° C., and a crystal melting peak temperature (Tmα) derived from α crystal was detected at 168 ° C.
That is, βPP-1 has β activity, and the β activity calculated from the following formula was 80%.
β activity (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100
ΔHmβ: Crystal heat of fusion derived from β crystal detected in the range of 145 ° C. or higher and lower than 160 ° C. ΔHmα: Crystal heat of fusion derived from α crystal detected from 160 ° C. or higher and 175 ° C. or lower; βPP-2: β crystal nucleating agent Pellets of “Bepol B-022SP (trade name)” (MFR 0.3 g / 10 min) manufactured by Aristech, which is a blended polypropylene resin, were used.
At the time of reheating, the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene was detected at 151 ° C., and the crystal melting peak temperature (Tmα) derived from the α crystal was detected at 169 ° C.
That is, βPP-2 has β activity, and the β activity calculated from the above formula was 78%.

(B) Thermoplastic resin (HM resin) having a crystal melting peak temperature of 170 ° C. or higher.
SPS: Idemitsu Kosan Co., Ltd. Syndiotactic polystyrene “ZAREC 90Z (trade name)” (Tm 272 ° C., density 1.04 g / cm ³ )
PBT: Polybutylene terephthalate “Duracon 600FP (trade name)” manufactured by Polyplastics Co., Ltd. (Tm 224 ° C., density 1.43 g / cm ³ )
・ PMP: Polymethylpentene “TPX 18R (trade name)” manufactured by Mitsui Chemicals
(Tm237 ° C., density 0.833 g / cm ³ )
(C) Thermoplastic resin other than HM resin / HDPE: High-density polyethylene “Hi-Zex HZ2200J (trade name)” manufactured by Prime Polymer Co., Ltd. (Tm 134 ° C., density 0.964 g / cm ³ )

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

(1) Layer ratio 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) Breakdown temperature The obtained film was cut into 60 mm × 60 mm square, and as shown in FIG. 2 (A), an aluminum plate (material: JIS standard A5052) with a 40 mmφ circular hole in the center. , Size: 60mm long, 60mm wide, 1mm thick) sandwiched between two sheets and restrained by a clip (manufactured by KOKUYO, double clip “Kuri-J35 (trade name)”) as shown in FIG. 2 (B) did.
An oven (Tabai Espec Co., Ltd., Tabai Giao, Inc.) set to a temperature of 150 ° C or higher in increments of 5 ° C (150 ° C, 155 ° C, 160 ° C, 165 ° C ...). -Bun "GPH200", damper closed state) After the oven internal temperature rose to each temperature, the oven was held for 3 minutes, then taken out and cooled, and the film breaking state was observed. The temperature at which film breakage was observed was taken as the breakdown temperature.
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.

(3) Pin puncture strength According to Japanese Agricultural Standards Notification No. 1019, the pin puncture strength was measured under the conditions of a pin diameter of 1.0 mm, a tip portion of 0.5R, and a pin puncture speed of 300 mm / min.
“◎” when the pin puncture strength is 3.0N or more, “◯” when the pin puncture strength is 1.5N or more and less than 3.0N, and “X” when the pin puncture strength is less than 1.5N. It was evaluated.

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

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

(7) Porosity The porosity is a numerical value indicating the proportion of the space portion in the porous film. The porosity was determined by measuring the substantial amount W1 of the porous film, calculating the mass W0 when the porosity was 0% from the density and thickness of the resin composition, and calculating from these values based on the following formula.
Porosity Pv (%) = {(W0−W1) / W0} × 100

(8) 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 PerkinElmer, and then held for 240 minutes. The temperature was lowered from 10 ° C. to 25 ° C. at a cooling rate of 10 ° C./min, 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 a peak was detected at 145 ° C. to 160 ° C., which is the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene at the time of reheating.
○: When Tmβ is detected within the range of 145 ° C to 160 ° C (with β activity)
X: When Tmβ is not detected within the range of 145 ° C to 160 ° C (no β activity)
Note that the β activity was measured with a sample amount of 10 mg and the atmosphere gas as nitrogen.

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

Comparative Example 1 in which the thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher was not mixed with the composition of the first layer had a breakdown temperature of 190 ° C. and did not exhibit sufficient breakdown characteristics. Moreover, the comparative example 2 which consists of a single layer porous film of a polypropylene-type resin had a breakdown temperature of 195 degreeC, and did not express sufficient breakdown characteristics.
Comparative Example 3 consisting only of the first layer formed of a composition in which a mixed resin of a polypropylene resin and a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher is mixed has a low pin puncture strength of 1.10 N. The mechanical strength was low.
On the other hand, the laminated porous film of the example constituted within the range defined in the present invention has an excellent breakdown characteristic with a breakdown temperature of 235 ° C. or more, and has mechanical strength, It also had excellent air permeability and was excellent.

  Since the laminated porous film produced by the production method of the present invention has excellent air permeability, mechanical strength and heat resistance, it can be suitably used for a battery separator.

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

Claims (10)

A laminated porous stretched film having at least a first layer and a second porous layer,
The first layer is a layer made of a resin composition obtained by mixing a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher with a polypropylene resin containing a β crystal nucleating agent made of an amide compound .
The second layer comprises a resin composition in which a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher is not mixed with a polypropylene resin in which a β crystal nucleating agent composed of an amide compound is blended, and β activity and / Or a layer having β-crystal formation power,
A laminated porous stretched film having an air permeability resistance of 1 to 10,000 seconds / 100 ml, a pin puncture strength of 1.5 N or more, and a breakdown temperature of 200 ° C. or more.   2. The resin composition constituting the second layer, 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. Laminated porous stretched film.   3. The laminated porous structure according to claim 1, wherein the polypropylene resin has Mw / Mn of 2.0 to 10.0 and a melt flow rate (MFR) of 0.5 to 15 g / 10 minutes. Stretched film.   The laminated porous stretched film according to any one of claims 1 to 3, wherein the polypropylene resin is homopolypropylene.   The resin composition which comprises the said 1st layer WHEREIN: The mixing mass ratio of the said polypropylene resin and the thermoplastic resin whose crystal melting peak temperature is 170 degreeC or more is 10-90 / 90-10. The laminated porous stretched film according to any one of claims 1 to 4.   The thermoplastic resin having a crystal melting peak temperature of 170 ° C or higher is at least one selected from the group consisting of polyester resins, polystyrene resins, fluorine resins, and polymethylpentene resins. Item 6. The laminated porous stretched film according to any one of items 5.   The laminated porous stretched film according to any one of claims 1 to 6, which has a three-layer structure in which the first layer is an intermediate layer and the second layer is both outer layers.   The laminated porous stretched film according to any one of claims 1 to 7, wherein a pin penetration strength per 1 µm thickness is 0.092 N / µm or more and 0.0148 N / µm or less.   A battery separator comprising the laminated porous stretched film according to any one of claims 1 to 8, and having an air resistance of 5 to 3000 seconds / ml.   A battery in which the battery separator according to claim 9 is incorporated.