JP5144883B2 - Propylene (co) polymer composition - Google Patents

Description

  The present invention relates to a propylene (co) polymer composition obtained by adding a phosphate metal salt to a mixture of a specific range of two types of propylene (co) polymers having different melt flow rates. When the propylene (co) polymer composition of the present invention is used, a molded article having excellent transparency can be obtained.

  Crystalline synthetic resins such as polyolefin resins such as polypropylene and polyethylene, and polyester resins such as polyethylene terephthalate and polybutylene terephthalate are aluminum pt-butylbenzoate, dibenzylidene sorbitols, aromatic phosphate metal salts, bicyclo [2 , 2,1] heptene-1,2-carboxylic acid metal salt, bicyclo [2,2,1] heptane-1,2-carboxylic acid metal salt, etc. Thus, it is known that the molding cycle is improved by improving the transparency and mechanical properties and increasing the crystallization speed.

  The aromatic phosphate metal salt used in the present invention is widely used as a nucleating agent for improving the crystallization temperature, transparency and mechanical properties of a crystalline synthetic resin. JP-A-58-1736 proposes a metal salt of an aromatic cyclic phosphate, and JP-A-5-1556078 discloses a metal salt of an aromatic cyclic phosphate and an alkali metal fatty acid salt. It has been proposed to function as a nucleating agent with a greater effect of improving physical properties by using in combination (see Patent Documents 1 and 2).

  On the other hand, research on the monomer sequence of the resin has been conducted, and the sustainability ratio of the block structure in the propylene copolymer is defined (see Non-Patent Document 1).

  In particular, although propylene-based resins are excellent in heat resistance, etc., dibenzylidene sorbitols that have low transparency and excellent transparency improvement effects are thermally decomposed to produce an aldehyde odor, so there is no problem of odor and excellent transparency. A propylene-based resin that gives a molded product is desired.

JP 58-1736 A (Claims) JP-A-5-1556078 (Claims) Basics of polymer experiments-Molecular characterization p. 359 (Kyoritsu Publishing, Polymer Society)

  Provided is a propylene (co) polymer composition which gives a molded article having no odor problem and excellent transparency.

  As a result of intensive studies in view of the above situation, the present inventors have found that an aromatic phosphate metal is mixed with a propylene (co) polymer mixture obtained by mixing two types of propylene (co) polymers having a specific range of melting characteristics. It has been found that by adding a salt, a propylene (co) polymer composition can be obtained which gives a molded article which is free from odor problems and is particularly excellent in transparency.

That is, the present invention is represented by the following general formula (1), a melt flow rate in JIS K 7210 (MFR) (1.85 kg load at 230 ° C.), and, you express the following general formula (2) Soft In a mixture in which a propylene (co) polymer (PP-A) having a conversion point (Ts) and a propylene (co) polymer (PP-B) were mixed so as to have a mass ratio represented by the following formula (3) a propylene (co) polymer set forming material characterized by comprising the addition of an aromatic phosphoric acid ester metal salt represented by the following general formula (I).
0.5 <log (MFR (PP-A) / MFR (PP-B)) <2 (1)
However, MFR (PP-A) and MFR (PP-B) are 0.01-35 dg / min.
| Ts (PP-A) -Ts (PP-B) | <25 (° C.) (2)
(PP-A) / (PP-B) = 95 / 5-80 / 20 (3)

However, R ₁ in the formula is an alkyl group having 4-8 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, _{R 3} is an alkylidene group having 1 to 4 carbon atoms, A is (n + x) valent metals, n represents the number of 1 to 3, x is a number from 0-2.

At least one of the propylene (co) polymers preferably contains 0.1 to 5 mol% of a copolymer monomer composed of one or more of ethylene or an α-olefin having 4 or more carbon atoms.

At least one of the propylene (co) polymers contains 0.1 to 5 mol% of a copolymer monomer composed of one or more of ethylene or an α-olefin having 4 or more carbon atoms, and is represented by the following formula. It is preferable that the sustaining ratio (ρ) of the copolymerizable monomer is 1 or less.
ρ = R _ran / R
In the above formula, R represents the number of chain transitions per 100 monomer units, and R _ran represents the value of R when ethylene is statistically randomly inserted .

Propylene (co) polymer composition of the present invention further contains Mukoto a composite metal salt containing a lithium salt and / or lithium organic acids are preferred.

Furthermore, the organic lithium salt is preferably a fatty acid lithium salt and / or hydroxy fatty acid lithium salt.

  With the propylene (co) polymer composition of the present invention, a molded article having no odor problem and excellent transparency can be obtained.

  The two types of propylene (co) polymers used in the present invention are a propylene (co) polymer (PP-A) and a propylene (co) polymer (PP-B), each of propylene homopolymer or propylene. A copolymer is used. Examples of the comonomer used in the copolymer include ethylene or α-olefin, and examples of the α-olefin include butene-1, pentene-1, hexene-1, 3-methylbutene-1, and the like. Examples include binary copolymers such as propylene-ethylene copolymer and propylene-butene copolymer, and ternary copolymers such as propylene-ethylene-butene copolymer.

  As the propylene (co) polymer used in the present invention, at least one, that is, a copolymer containing 0.1 to 5 mol%, preferably 0.3 to 3 mol% of a copolymer component is contained on one side. preferable. When the copolymerization monomer is less than 0.1 mol%, the properties as a copolymer cannot be obtained, and when it exceeds 5 mol%, the transparency improving effect by the compound of the general formula (I) is small.

Further, the propylene (co) polymer used in the present invention needs to satisfy the following general formula (1) in the ratio of melt flow rate (MFR) (1.85 kg load at 230 ° C. ) in JIS K7210 .
0.5 <log (MFR (PP-A) / MFR (PP-B)) <2 (1)
However, PP-A and PP-B each melt flow rate is required to be 0.01~35dg / min, more preferably 0.05 to 25 dg / min. The above range of melt flow rate processability productivity is lowered is less than 0.01 dg / min, small to 35 dg / min is greater than the effect of the transparency improvement by compounds of general formula (I) Kunar.
Further, the propylene (co) melt flow rate of the polymer (PP-A) is 0.3~25dg / min, a melt flow rate of propylene (co) polymer (PP-B) is 0.05～20Dg / Particularly preferred is min.

Moreover, the softening point of each propylene (co) polymer used for this invention satisfy | fills Formula (2).
| Ts (PP-A) -Ts (PP-B) | <25 (° C.) (2)
The difference between the softening points is preferably 20 ° C. or less.
When a propylene (co) polymer having a softening point difference of 25 ° C. or higher is mixed, the components are separated into individual components during processing, resulting in a decrease in transparency and a decrease in physical properties.

The blending mass ratio of the propylene (co) polymer (PP-A) and the propylene (co) polymer (PP-B) used in the present invention is in the range of the formula (3).
(PP-A) / (PP-B) = 95 / 5-80 / 20 (3)
The blending mass ratio is preferably 93/7 to 85/15.
Outside this range, the effect of improving the transparency is small, and the workability is also lowered.

  The sustainability ratio (ρ) of at least one of the propylene (co) polymers used in the present invention, preferably the propylene (co) polymer (PP-B), is preferably 1 or less, and is 0.99. Smaller ones are particularly preferred. When it is larger than 1, the effect of improving transparency by the compound of the general formula (I) is small.

  The ratio indicating the molecular weight distribution of the propylene (co) polymer mixture, the weight average molecular weight / number average molecular weight is preferably in the range of 4 to 10, more preferably 4 to 6, and particularly preferably 4 to 5. If it is less than 4, the effect of improving the transparency of the compound of the general formula (I) is small, and if it is more than 10, the transparency is lowered by a low molecular weight component having a high comonomer content such as ethylene.

  In the present invention, the propylene (co) polymer (PP-A) and the propylene (co) polymer (PP-B) are each a single propylene within the range satisfying the conditions (1) to (3). It may be a (co) polymer or a mixture of two or more propylene (co) polymers.

  With respect to the propylene (co) polymer, there are no particular limitations on the stereoregularity, specific gravity, type of polymerization catalyst, presence or absence or degree of removal of the polymerization catalyst, polymerization conditions such as temperature and pressure, and the like.

The phosphate metal salt used in the present invention is represented by the general formula (I).
Examples of the alkyl group having 4 to 8 carbon atoms represented by R ₁ in the general formula (I) include butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, and octyl. , Isooctyl, tertiary octyl and the like. The number of carbon atoms of the alkyl group represented by R ₁ is preferably 4 or 5.

R ₂ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group represented by R ₂ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, and tertiary. Examples include octyl. The carbon number of the alkyl group of R ₂ is preferably 1 to 5.

R ₃ represents an alkylidene group having 1 to 4 carbon atoms. Examples of the alkylidene group represented by R ₃ include methylene, ethylidene, propylidene, and butylidene. R ₃ is preferably methylene.

The compound represented by the general formula (I) used in the present invention has chemical properties such as physical properties such as average particle diameter, average aspect ratio and bulk specific gravity, crystal structure, chlorine content, and presence or absence of crystal water. The average particle size is 10 μm or less, particularly 5 μm or less, the average aspect ratio is 10 or less, particularly 5 or less, the bulk specific gravity is 0.1 or more, and the chlorine content is 100 ppm or less, particularly 30 ppm or less. Preferably there is. When the average particle size is large, the mechanical properties of the resulting propylene (co) polymer composition are not improved so much, and when formed into a film or a thin sheet, it causes poor appearance and reduced strength. When the average particle size is small, the mechanical properties of the resulting propylene (co) polymer composition are improved. However, since handling such as generation of dust becomes difficult, it is preferable to granulate or masterbatch. When the average aspect ratio is large, undesired phenomena such as mechanical properties of the obtained molded product differ depending on the direction. If the bulk specific gravity is small, the handling as a powder becomes worse, such as difficulty in automatic light weight, low fluidity, and difficulty in keeping the supply speed to the processing machine constant. Moreover, when the chlorine content increases, the resulting propylene (co) polymer composition is colored.

  As a method for producing an aromatic phosphate metal salt for controlling physical properties within a preferred specific range, an aromatic phosphate metal salt synthesized by a conventionally known method is used for ball mill, Henschel, kneader, etc. It can manufacture by grind | pulverizing using a grinder. Further, the chemical characteristics can be controlled by a purification process such as repeating the washing process.

  As the aromatic phosphate metal salt represented by the general formula (I), more specifically, the following No. 1 1-6 compounds, etc. are mentioned. However, the present invention is not limited by the following compounds.

Compound No. 1

Compound No. 2

Compound No. 3

Compound No. 4

Compound No. 5

Compound No. 6

In the propylene (co) polymer composition of the present invention, an alkali metal fatty acid salt may be used in combination as a nucleating agent. Examples of the alkali metal include lithium, sodium, and potassium, and lithium that is particularly excellent in the effect of improving transparency is preferable. Examples of the fatty acid include octylic acid, nonylic acid, decanoic acid, undecanoic acid, larulinic acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid and the like.
The combined ratio of the alkali metal fatty acid salt is 10 parts by mass or less, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin (propylene (co) polymer mixture. The same shall apply hereinafter). is there.
Transparency can be improved by the above combination.

  The propylene (co) polymer composition of the present invention comprises, as necessary, an antioxidant such as a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, a hydroxyamine antioxidant, and an ultraviolet absorber. It is preferable to use a hindered amine light stabilizer and another nucleating agent in combination. These additives may be blended individually into the resin or may be granulated or master batched together with the nucleating agent component. In addition to the main effects such as a stabilizing effect, the combination used in combination is selected in consideration of not impairing the effects of the present invention in terms of odor and transparency.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4- Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethy Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2- Tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [1,1-dimethyl-2- { (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] Ndecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like, and 0.001 to 10 parts by mass, more preferably 0.05-5 parts by weight are used.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4). -Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,4,6-tritert-butylphenyl) pentaerythritol di Sphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl- 5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) ) Biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite 2,2′-methylenebis (4,6-tert-butylphenyl) -octa Silphosphite, 2,2′-ethylidenebis (4,6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol phosphite .

  Examples of thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters.

  Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methyle 2- (2′-hydroxyphenyl) such as bis (4-tert-octyl-6-benzotriazolyl) phenol and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole ) Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5- Benzoates such as di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyl Substituted oxanilides such as oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2 Cyanoacrylates such as cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) ) -S-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6- And triaryltriazines such as bis (2,4-ditert-butylphenyl) -s-triazine.

  Examples of hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2 , 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2, , 6-Pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl 2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4- Jiku Rho-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl- 4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylaminoundecane, 1,6,11-tris [2, 4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4 Hindered amine compounds such as -piperidyl) amino) -s-triazin-6-ylaminoundecane.

Other nucleating agents include metal salts of benzoic acids such as aluminum-p-tert-butylbenzoate and lithium-p-tert-butylbenzoate; dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, bis (4- Benzylidene sorbitols such as ethylbenzylidene) sorbitol and bis (dimethylbenzylidene) sorbitol; metal alcoholates such as glycerin zinc; amino acid metal salts such as zinc glutamate; Examples thereof include acids and metal salts thereof.
The combined use ratio of the other nucleating agent is 100 parts by mass or less, preferably 3 to 50 parts by mass with respect to 100 parts by mass of the phosphate ester metal salt represented by the general formula (I).

  In addition, the composition of the present invention may contain hydrotalcite, calcium stearate, magnesium stearate and other alkaline earth metal fatty acid salts, flame retardants, heavy metal deactivators, antistatic agents, fillers, if necessary. A lubricant such as ethylene bisstearylamide or erucic acid amide may be blended.

As the hydrotalcite, a compound represented by the following general formula (V) or a compound obtained by substituting a part of the carbonate anion of the compound represented by the following formula with perchloric acid or the like is used.
_{Zn p Mg q Al r CO 3} (OH) (2p + 2q + 3r-2) · nH 2 O (V)
(Wherein p represents 0 ≦ p ≦ 4, q represents 2 ≦ q ≦ 6, r represents 1 ≦ r ≦ 3, and n represents 0 ≦ n ≦ 20)

  Flame retardants include condensed flame retardants such as halogen flame retardants such as decabromodiphenyl ether and tetrabromobisphenol A, polyphenols such as triphenyl phosphate, resorcinol and bisphenol A, and monohydric phenols such as phenol and 2,6-xylenol. Acid esters; inorganic phosphorus compounds such as red phosphorus and melamine phosphate; nitrogen-containing flame retardants such as melamine cyanurate; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; flame retardant aids such as antimony oxide and zirconium oxide An anti-drip agent such as polytetrafluoroethylene is used.

  Examples of the heavy metal deactivator include 2-hydroxybenzamide-N-1H-1,2,4-triazol-3-yl and dodecandioic acid bis [2- (2-hydroxybenzoyl) hydrazide]. It is done.

  The propylene (co) polymer composition of the present invention has a remarkable effect when the molding temperature is 200 ° C. or lower. Examples of the molding method include injection molding, blow molding, extrusion molding, compression molding, stretched film molding, and calendar molding. Preferably, injection molding and blow molding are used.

  The propylene copolymer composition of the present invention can be used in various applications such as building materials, agricultural materials, automobile parts, packaging materials, sundries, toys, home appliances, and medical instruments. In particular, since it has a high degree of transparency, it is suitably used for medical applications such as infusion bags, syringes, and drug solution-filled syringes, and films.

(Example)
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.

As a propylene (co) polymer (PP-A), a propylene copolymer (ethylene content 4.0 mol%) having a melt flow rate of 20 dg / min, ρ = 1.01, and a softening point of 140 ° C. A propylene copolymer (ethylene content 2.1 mol%) having a melt flow rate of 2 dg / min, ρ = 0.97, and a softening point of 143 ° C. was used as the polymer (PP-B), and (PP-A) / (PP -B) = 90/10 (mass ratio) and mixed to obtain a propylene copolymer mixture (a).
The propylene copolymer mixture (a) satisfies the following conditions.
| Ts (PP-A) −Ts (PP-B) | = 3 ° C.
log (MFR (PP-A) / MFR (PP-B)) = 1,
Melt flow rate 18dg / min, and Mw / Mn = 4.7
100 parts by mass of the propylene copolymer mixture (a), 0.1 parts by mass of calcium stearate, 0.1 parts by mass of tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane Part, tris (2,4-ditert-butylphenyl) phosphite 0.1 part by mass, compound No. 3 was blended with 0.1 part by weight of lithium myristate and 0.1 part by weight of lithium myristate using a Henschel mixer and extruded at 240 ° C. to give pellets. This pellet was injection-molded at 200 ° C. to produce a sheet-like test piece. The test piece thus obtained was measured for degree (%) based on ASTM D-1003-61. The results are shown in Table 1.
Moreover, although 10 g of pellets were put in a glass bottle and a sensory test was conducted by 10 persons for the odor after 24 hours in a 100 ° C. oven, none of the pellets in the following examples had any odor.

As a propylene copolymer mixture, a propylene copolymer (PP-A) having a melt flow rate of 20 dg / min, ρ = 1.01, a softening point of 140 ° C. (ethylene content: 4.0 mol%) ) As a propylene (co) polymer (PP-B) using a propylene homopolymer (ethylene content 0.0 mol%) having a melt flow rate of 2 dg / min, ρ = 0.98, and a softening point of 160 ° C. It mixed by PP-A) / (PP-B) = 90/10 (mass ratio), and the propylene copolymer mixture (b) was obtained.
The propylene copolymer mixture (b) satisfies the following conditions.
| Tm (PP-A) -Tm (PP-B) | = 20 ° C.
log (MFR (PP-A) / MFR (PP-B)) = 1,
Melt flow rate 18dg / min, and Mw / Mn = 4.7
A test piece was prepared and evaluated in the same manner as in Example 1 except that 100 parts by mass of the propylene copolymer mixture (b) was used. The results are shown in Table 1.

  As a nucleating agent, Compound No. A test piece was prepared and evaluated in the same manner as in Example 1 except that a mixture of 0.15 part by weight of 1 and 0.05 part by weight of lithium hydroxystearate was used. The results are shown in Table 1.

  As a nucleating agent, Compound No. A test piece was prepared and evaluated in the same manner as in Example 2 except that 0.15 part by weight of 1 and 0.05 part by weight of lithium hydroxystearate were used. The results are shown in Table 1.

(Comparative Example 1)
Instead of the propylene copolymer mixture (a), one type of propylene copolymer having an melt flow rate of 18 dg / min, ρ = 0.99, a softening point of 141 ° C., and Mw / Mn = 4.0 (ethylene content 2) .1 mol%) A test piece was prepared and evaluated in the same manner as in Example 1 except that 100 parts by mass were used. The results are shown in Table 1.

(Comparative Example 2)
As a nucleating agent, Compound No. A test piece was prepared and evaluated in the same manner as in Comparative Example 1 except that 0.15 parts by mass of 1 and 0.05 parts by mass of lithium hydroxystearate were used. The results are shown in Table 1.

(Comparative Example 3)
Instead of the propylene copolymer mixture (a), 100 parts by mass of one type of propylene copolymer having a melt flow rate of 15 dg / min, ρ = 0.99, a softening point of 142 ° C., and Mw / Mn = 4.5 (ethylene A test piece was prepared and evaluated in the same manner as in Example 1 except that the content was 2.1 mol%. The results are shown in Table 1.

(Comparative Example 4)
As a propylene copolymer mixture, a propylene copolymer (PP-A) having a melt flow rate of 20 dg / min, ρ = 1.01, a softening point of 140 ° C. (ethylene content: 4.0 mol%) ) As a propylene (co) polymer (PP-B) using a propylene copolymer (ethylene content 2.1 mol%) having a melt flow rate of 15 dg / min, ρ = 0.98, and a softening point of 142 ° C. It mixed by PP-A) / (PP-B) = 90/10 (mass ratio), and the propylene copolymer mixture (d) was obtained.
The propylene copolymer mixture (d) satisfies the following conditions.
| Tm (PP-A) -Tm (PP-B) | = 2 ° C.
log (MFR (PP-A) / MFR (PP-B)) = 0.12.
Melt flow rate 15 dg / min, and Mw / Mn = 5.0
A test piece was prepared and evaluated in the same manner as in Example 1 except that 100 parts by mass of the propylene copolymer mixture (d) was used. The results are shown in Table 1.

(Comparative Example 5)
Instead of the propylene copolymer mixture (a), one type of propylene copolymer (ethylene content 2) having a melt flow rate of 20 dg / min, ρ = 0.99, a softening point of 140 ° C., and Mw / Mn = 4.0. .1 mol%) A test piece was prepared and evaluated in the same manner as in Example 1 except that 100 parts by mass were used. The results are shown in Table 1.

* 1: Compound No. 3 and lithium myristate * 2: Compound No. Mixture of 1 and 12-hydroxy hydroxystearate

Claims (5)

Represented by the following general formula (1), a melt flow rate in JIS K 7210 (1.85 kg load at 230 ° C.) (MFR), and, softening point represented Ru by the following general formula (2) (Ts) A mixture of propylene (co) polymer (PP-A) and propylene (co) polymer (PP-B) having a mass ratio represented by the following formula (3) is mixed with the following general formula (I propylene characterized by comprising the addition of an aromatic phosphoric acid ester metal salt represented by) (co) polymer set Narubutsu;
0.5 <log (MFR (PP-A) / MFR (PP-B)) <2 (1)
However, MFR (PP-A) and MFR (PP-B) are 0.01-35 dg / min;
| Ts (PP-A) -Ts (PP-B) | <25 (° C.) (2)
(PP-A) / (PP-B) = 95 / 5-80 / 20 (3)
Where R ₁ is an alkyl group having 4 to 8 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₃ is an alkylidene group having 1 to 4 carbon atoms, and A is (N + x) valent metal, n represents a number of 1 to 3, and x represents a number of 0 to 2.   At least one of the propylene (co) polymers contains 0.1 to 5 mol% of at least one copolymer monomer selected from the group consisting of ethylene and an α-olefin having 4 or more carbon atoms. The propylene (co) polymer composition according to claim 1. At least one of the propylene (co) polymers contains 0.1 to 5 mol% of at least one copolymer monomer selected from the group consisting of ethylene and an α-olefin having 4 or more carbon atoms. A propylene (co) polymer composition according to claim 1 or 2, wherein the sustaining ratio (ρ) of the copolymerizable monomer represented by the following formula is 1 or less;
ρ = Rran / R
In the above formula, R represents the number of chain transitions per 100 monomer units, and Rran represents the value of R when ethylene is statistically randomly inserted.   The propylene (co) polymer composition according to any one of claims 1 to 3, further comprising an organic acid lithium salt and / or a composite metal salt containing lithium.   The propylene (co) polymer composition according to claim 4, wherein the organic acid lithium salt is a fatty acid lithium salt and / or a hydroxy fatty acid lithium salt.