JPH10251463A - Propylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene resin compsn. which is excellent in clarity and stiffness and hardly emits odor. SOLUTION: This compsn. is prepd. by compounding 0.03-2 pts.wt. metal salt of rosin with 100 pts.wt. propylene polymer comprising 100-90mol% units derived from propylene and 0-10mol% units derived from ethylene and/or a 4-20C α-olefin and having a mol.wt. distribution (Mw/Mn) of 1.5-4, an average elution temp. (T50 ) of 75-120 deg.C, and an elution dispersity (σ) of 9 or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene resin composition which is excellent in transparency and rigidity and has low odor.

[0002]

2. Description of the Related Art Conventionally, propylene-based resins such as polypropylene are excellent in moldability and rigidity, and are also excellent in hygiene and heat resistance.
Like other resins such as vinyl chloride resin and polystyrene resin, they are widely used for various purposes such as daily necessities and food containers. In particular, the propylene-based resin is crystalline, and has excellent heat resistance as compared with a vinyl chloride resin and a polystyrene-based resin. However, since the propylene-based resin is crystalline as described above, it has a drawback that transparency is inferior to vinyl chloride resin and polystyrene-based resin.

[0003]

Accordingly, as one of techniques for improving the transparency of such a propylene-based resin, a method of copolymerizing propylene and ethylene using a titanium-based catalyst is generally known. However, such techniques improve transparency, but require the addition of a significant amount of ethylene during copolymerization, resulting in lower crystallinity and greater rigidity in the resulting copolymer. The disadvantage of this is that it causes. On the other hand, as a method of improving transparency other than the above, a method of blending various nucleating agents is known,
As the nucleating agent used here, an inorganic substance, an aromatic carboxylate, an aromatic phosphate, and a sorbitol derivative are used. Among these nucleating agents, those containing a sorbitol derivative can be the resin having the most excellent transparency, however, the sorbitol derivative sublimates during molding and contaminates the mold, The problem of generating odors arises. Further, when a nucleating agent such as an aromatic carboxylate or a metal salt of an aromatic phosphoric acid is used among the above nucleating agents, there is a problem that the effect of improving transparency is insufficient.

[0004]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventor has found that by blending a specific compound with a propylene polymer having specific physical properties, transparency and rigidity can be improved. The present invention has been completed based on the finding that a propylene-based resin composition having excellent and low odor can be obtained. That is, the propylene resin composition of the present invention has a metal salt of a rosin of 0.03 to 100 parts by weight based on a propylene polymer having the following physical properties (a) to (c).
2 parts by weight are blended. Physical property (a): 100 structural units obtained from propylene
~ 90 mol%, ethylene and / or α having 4 to 20 carbon atoms
-The structural unit obtained from the olefin is a propylene-based polymer having 0 to 10 mol% Physical properties (b): The molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4 Physical properties (c): The average dissolution temperature (T ₅₀ ) is in the range of 75 to 120 ° C., and the dissolution degree (σ) is 9 or less.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION

[I] Constituent (1) Propylene Polymer (A) Physical Properties It is important that the propylene polymer constituting the propylene resin composition of the present invention has the following physical properties (a) to (c). is there. Physical property (a): 100 structural units obtained from propylene
~ 90 mol%, ethylene and / or α having 4 to 20 carbon atoms
-The structural unit obtained from the olefin is a propylene-based polymer having 0 to 10 mol% Physical properties (b): The molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4 Physical properties (c): The average dissolution temperature (T ₅₀ ) is in the range of 75 to 120 ° C., and the dissolution degree (σ) is 9 or less.

(A) Structure The propylene polymer constituting the propylene resin composition of the present invention is a propylene homopolymer or a copolymer of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms. A random copolymer is used. In the propylene-based polymer, one structural unit obtained from propylene is used.
0 to 90 mol%, preferably 100 to 92 mol%, and 0 to 10 mol%, preferably 0 to 8 mol% of a structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms.
It is important that it is contained in the proportion of mol%. The comonomer ethylene and / or copolymerized with propylene
Alternatively, specific examples of the α-olefin having 4 to 20 carbon atoms include ethylene, butene-1, pentene-1, hexene-1, octene-1, and 4-methylpentene-1. If the structural unit of the comonomer exceeds the above range, the rigidity is greatly reduced, and practicality is impaired. The structural unit obtained from propylene in the propylene-based polymer and the structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms are measured using ¹³ C-NMR (nuclear magnetic resonance method). Value. Specifically, FT-NMR 2 manufactured by JEOL Ltd.
This is a value measured by a 70 MHz device.

(B) Molecular weight distribution (Mw / Mn) The propylene-based polymer has a molecular weight distribution (Mw / Mn).
It is important that Mn) be in the range of 1.5-4, preferably 2-3.5. If the molecular weight distribution (Mw / Mn) is less than the above range, the moldability will be poor, and if it exceeds the above range, the transparency will deteriorate. The molecular weight distribution (M
w / Mn) is a value measured using a GPC measuring device. Specifically, WATERS 150-C ALC
/ GPC.

(C) Average Elution Temperature (T ₅₀ ) and Elution Dispersion (σ) Further, the propylene-based polymer is subjected to temperature rising elution fractionation (TREF: Temperature Rising Elution Fraction).
The average elution temperature (T ₅₀ ) of the elution curve obtained by
It is important that the temperature is in the range of 5 to 120 ° C., preferably 80 to 120 ° C., and the dissolution degree (σ) is 9 or less, preferably 8 or less.

Average Elution Temperature (T ₅₀ ) The average elution temperature (T ₅₀ ) indicates the temperature at which the cumulative weight of the eluted polymer becomes 50%. If the average elution temperature (T ₅₀ ) is less than the above range, the molecular weight is too low,
Because the melting point is too low, it causes insufficient rigidity. Also,
If it exceeds the above range, the molecular weight will be too high or the melting point will be too high, making molding difficult.

Dissolution degree of dispersion (σ) The dissolution degree of dispersion (σ) is expressed by the following formula (1):
The temperature at which the cumulative weight of the eluted polymer becomes 15.9% (T
_15.9 ) and the temperature at which the eluted polymer becomes 84.1% (T
_81.4 ). σ = T _81.4 −T _15.9 (1) When the dissolution degree of dispersion (σ) exceeds the above range, components having poor stereoregularity and significantly different comonomer compositions, which hinder crystallinity, increase, resulting in rigidity and transparency. A propylene-based resin composition having excellent properties cannot be obtained.

Measurement of Elution Curve by Temperature-Increasing Elution Fractionation In the measurement of temperature-elution elution fractionation (TREF), a polymer is completely dissolved once at a high temperature and then cooled to form a thin polymer layer on the surface of an inert carrier. Next, the temperature is continuously or stepwise raised, the eluted components are collected, the concentration is continuously detected, and a graph (elution curve) drawn based on the elution amount and the elution temperature is shown. Can be measured. Temperature rise elution fractionation (TRE
For details of the measurement of F), see Journal of
Applied Polymer Science, Vol. 26, pp. 4217-4231 (1981).

(D) MFR The propylene polymer used in the propylene resin composition of the present invention has an MFR of JIS-K7210.
(230 ° C., 2.16 kg load), 0.5 to 100 g / 10 min, especially 1 to 80 g / min.
Preferably, it is 10 minutes. If the MFR is higher than the above range, the impact strength of the product tends to be insufficient, and if the MFR is lower than the above range, poor flow tends to occur during molding.

[0013] (e) bending the propylene resin composition of the elastic modulus the present invention has a flexural modulus is 5,000~20,000kg / cm ² is preferable, 6,000~18,000kg / cm ² Is preferred. When the flexural modulus exceeds the above range, a practical impact value cannot be obtained, and when the flexural modulus is below the above range, a molded article tends to be unable to be formed due to insufficient rigidity. The flexural modulus is JIS-
It is a value measured by K7203.

(B) Production (a) Metallocene Catalyst The propylene-based polymer comprises the components (A) and (B) described below, and the component (C) used as necessary.
, In the presence of a so-called metallocene catalyst. <Component (A)> The component (A), in the formula ^{_{Q 1 (C 5 H 4-}} a R 1 a) (C 5 H 4-b R 2
_b ) MeX ¹ Y ¹ wherein Q ¹ is a binding group bridging two conjugated five-membered ring ligands, and is a divalent hydrocarbon group having 1 to 20 carbon atoms, A silylene group having a hydrocarbon group, a germylene group having a hydrocarbon group having 1 to 20 carbon atoms,
e represents zirconium or hafnium; X ¹ and Y
¹ is each independently a hydrogen, a halogen group, a carbon number 1
To 20 hydrocarbon groups, an alkoxy group having 1 to 20 carbon atoms,
An alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms,
Or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. R
¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or
Indicate a boron-containing hydrocarbon group. In addition, two adjacent R ¹
Alternatively, R ² may be bonded to each other to form a ring. a and b are integers satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4. However, the two five-membered ring ligands having R ¹ and R ² are asymmetric with respect to the plane containing Me in terms of relative position via the group Q ¹ . ] It is a compound represented by these.

As described above, Q ¹ is a binding group bridging two conjugated five-membered ring ligands, and (A) a divalent group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. A hydrocarbon group, more specifically, for example, an unsaturated hydrocarbon group such as an alkylene group, a cycloalkylene group, or an arylene group, or (ii) a silylene group having a hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms. , (C) having 1 to 20 carbon atoms, preferably 1 carbon atom
And germylene groups having a hydrocarbon group. The distance between the two bonds of the divalent Q ¹ group is about 4 atoms or less when Q ¹ is a chain, regardless of the number of carbon atoms.
It is preferably 3 atoms or less, and when Q ¹ has a cyclic group, it is preferable that the cyclic group is about 2 atoms or less, preferably only the cyclic group.
Therefore, in the case of alkylene, ethylene and isopropylidene (the distance between both bonds is 2 atoms and 1 atom), and in the case of a cycloalkylene group, the cyclohexylene group (the distance between both bonds is only a cyclohexylene group), and alkylsilylene In the case of a group, a dimethylsilylene group (the distance between bonds is 1 atom) is preferred.

Me is zirconium or hafnium;
Preferably, it is zirconium. X ¹ and Y ¹ may be each independently, that is, they may be the same or different;
(A) hydrogen, (b) halogen (fluorine, chlorine, bromine,
Iodine, preferably chlorine), (c) a hydrocarbon group having 1 to 20 carbon atoms, (d) an alkoxy group having 1 to 20 carbon atoms,
(E) an alkylamide group having 1 to 20 carbon atoms, (f)
A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, (g) 1 carbon atom
To 20 to 20 silicon-containing hydrocarbon groups or (H) trifluoromethanesulfonic acid groups.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a nitrogen-containing hydrocarbon group. And a boron-containing hydrocarbon group. Further, two adjacent R ¹ or two R ² may be bonded to each other to form a ring. a and b are 0 ≦ a ≦ 4, 0 ≦ b
It is an integer satisfying ≦ 4.

As a specific example, see Japanese Patent Application Laid-Open No. 8-2087.
Compounds exemplified in JP-A No. 33 can be mentioned. For example, dimethylmylene bis (2,4-dimethylindenyl) zirconium dichloride, dimethylmylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, dimethylmylenebis (2-methyl-
4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, and the like. Among them, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride and dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride are preferably used.

<Component (B)> Component (B) is composed of component (B-1): an aluminum oxy compound, component (B-2): a Lewis acid, or component (B-3): component (A). An ionic compound capable of reacting to convert the component (A) into a cation can be mentioned. Some Lewis acids can be regarded as “ionic compounds capable of converting component (A) into cations by reacting with component (A)”.
Therefore, a compound belonging to both of the “Lewis acid and an ionic compound capable of converting the component (A) into a cation by reacting with the component (A)” is interpreted as belonging to one of the two. And

Of the component (B), the above component (B-1),
Specific compounds and production methods for component (B-2) and component (B-3) are exemplified by the compounds and production methods exemplified in JP-A-6-239914 and JP-A-8-208733. be able to. For example, the component (B-
Examples of 1) include methylalumoxane, ethylalumoxane, butylalumoxane, and isobutylalumoxane obtained from one type of trialkylaluminum and water, methylethylalumoxane obtained from two types of trialkylaluminum and water, and methylbutyl Examples of alumoxane, methylisobutylalumoxane, and alkylboronic acid include methylboronic acid, ethylboronic acid, butylboronic acid, and isobutylboronic acid.
Further, as the component (B-2), triphenylboron,
Organic boron compounds such as tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron can be exemplified. Furthermore, examples of the component (B-3) include triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and the like. Among them, methylalumoxane, isobutylalumoxane, triphenylcarbonium tetrakis (pentafluorophenyl) borate,
It is preferable to use N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

<Component (C): Organoaluminum compound>
Examples of the organoaluminum compound used as the component (C) include a compound represented by the general formula (AlR ⁴ _n X _3-n ) _{m wherein} R ⁴ represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; X represents a halogen, hydrogen, an alkoxy group, or an amino group. n is an integer of 1-3, preferably 2-3, and m is 1-2, preferably 1. And these compounds can be used alone or in combination of two or more. Specific compounds include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, trinormal decyl aluminum, diethyl aluminum monochloride, diethyl aluminum sesquialuminum Examples thereof include chloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like.
Of these, preferred are trialkylaluminum and dialkylaluminum hydrides wherein m = 1 and n = 3. More preferably, R ⁴ is trialkylaluminum having 1 to 8 carbon atoms.

<Formation of Catalyst> The catalyst used for producing the propylene-based polymer comprises the above-mentioned components (A) and (B), and optionally component (C). A so-called metallocene catalyst can be prepared by contacting the inside or outside of the polymerization tank with or without the monomer to be polymerized. The metallocene catalyst uses a particulate solid as a carrier, and can be used as a solid catalyst. Examples of the fine solid particles include inorganic porous oxides such as silica and alumina, ethylene, propylene, and the like.
Α-olefins such as -butene, or organic compounds such as polymers or copolymers formed mainly with styrene. The metallocene catalyst may be one obtained by pre-polymerization in the presence of an olefin. As the olefin used for the prepolymerization, propylene, ethylene, 1-butene, 3-methylbutene-
1, styrene, divinylbenzene and the like are used, but a mixture of these with another olefin may be used.

The amounts of component (A), component (B) and component (C) used in the preparation of the above metallocene catalyst are arbitrary, but are generally preferred depending on what is selected as component (B). The range of usage differs. When the above component (B-1) is used as the component (B), the atomic ratio (Al / Me) of the aluminum atom in the aluminum oxy compound of the component (B-1) to the transition metal in the component (A) is high. 1 to 10
It is in the range of 0000, preferably 10 to 10,000, more preferably 50 to 5,000. As the component (B), the Lewis acid of the component (B-2) or the component (B-
When the ionic compound 3) is used, the molar ratio of the transition metal in the component (B) to the components (B-2) and (B-3) is 0.1 to 1,000, preferably 0.1 to 1,000. It is used in the range of 5 to 100, particularly preferably 1 to 50. If the organoaluminum compound of the component (C) is used, the amount of the organoaluminum compound to be used is 10 moles per mole of the component (A).
It is preferably in the range of ⁵ or less, more preferably 10 ⁴ or less, particularly preferably 10 ³ or less.

(B) Polymerization The production of a propylene-based polymer using a so-called metallocene catalyst comprising the component (A), the component (B), and the component (C) used as required can be carried out by using propylene alone or , Propylene and ethylene or α- having 4 to 20 carbon atoms
It is carried out by contacting a mixture with an olefin. In the case of copolymerization, the quantitative ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change over time. Also,
Any of the monomers may be added in portions in consideration of the copolymerization reaction ratio.

As the polymerization mode, any method can be adopted as long as the catalyst component and each monomer are efficiently contacted. Specifically, a slurry method using an inert solvent, a slurry method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or substantially each monomer without substantially using a liquid solvent A gas phase method for maintaining a gaseous state or the like can be employed. Further, the present invention is also applied to continuous polymerization and batch polymerization. In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene can be used as a polymerization solvent.

As the polymerization conditions, the polymerization temperature is -78 to 1
The temperature is 60 ° C, preferably 0 to 150 ° C, and hydrogen can be used as a molecular weight regulator at that time. The polymerization pressure is from 0 to 90 kg / cm ² · G, preferably from 0 to 60 kg / cm ² · G, particularly preferably from 1 to 50 k / cm ² · G.
g / cm ² · G is appropriate. The propylene-based polymer has an MFR of 0.5 to 100 g / measured in accordance with JIS-K7210 (230 ° C., 2.16 kg load).
10 minutes, preferably 1 to 80 g / 10 minutes. MFR
Exceeds the above range, the impact strength of the product becomes insufficient and the MFR
If it is below the above range, poor flow tends to occur during molding.

(2) Metal salt of rosin The metal salt of rosin used in the propylene-based resin composition of the present invention is a reaction mixture produced by a reaction between a rosin and a metal compound. (A) Rosins The above rosins include gum rosin, tall oil rosin, or steam pine from raw pine tar to remove turpentine oil, or
Pine roots and pine wood are extracted with a solvent or sometimes extracted with an alkaline solution, natural rosins such as wood rosin obtained by acidification, or denatured, disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, Various modified rosins, such as polymerized rosin, α, β-ethylenically unsaturated carboxylic acid modified rosin, and purified rosin obtained by purifying these. The rosins are pimaric acid, sandaracobimaric acid,
It contains a plurality of resin acids selected from parastolic acid, isopimaric acid, abietic acid, dehydroabithienoic acid, neoabithienoic acid, dihydropimaric acid, dihydroabithienoic acid, tetrahydroabithienoic acid, and the like. In particular,
Generally, 30-40% by weight of abietic acid, 10-20% by weight of neoabietic acid, 14% by weight of dihydroabietic acid, 14% by weight of tetrahydroabietic acid, 8% by weight of d-pimaric acid, 8% by weight of iso-d-pimaric acid , Dehydroabietic acid, 5% by weight, levopimaric acid, 0.1% by weight, 80-97% by weight of a resin acid component, an unsaponifiable substance and other small amounts. The rosins have unsaturated bonds and have insufficient thermal stability. For the purpose of preventing the rosins, saturated rosins (hydrogenated rosins) reduced with hydrogen can be used.

(B) Metal The metal forming a metal salt with the above-mentioned rosin is 1 to 3
It is a valent metal ion, and specific examples thereof include metals such as alkali metals, alkaline earth metals, and aluminum. Among them, preferred metals include monovalent metal ions such as lithium, sodium, potassium, rubidium and cesium; divalent metal ions such as beryllium, magnesium, calcium, strontium, barium and zinc; and trivalent metals such as aluminum. Ions can be mentioned.
Among them, lithium, sodium, potassium, magnesium, calcium, and aluminum are preferably used, and particularly, lithium, sodium, and potassium are preferably used.

(C) Metal salt of rosin The metal salt formed from the rosin and a metal includes
It is a compound having a 1-3 valent metal element such as sodium, potassium, magnesium and the like, and forming a salt with the rosin, specifically, chlorides, nitrates, acetates of 1 to 3 valent metals , Sulfates, carbonates, oxides and the like. Among these metal salts of rosins, sodium salts, potassium salts, it is preferable to use at least one metal salt of rosins selected from magnesium salts,
Further, it is preferable to use a metal salt of at least one rosin selected from a metal salt of hydrogenated rosin, a metal salt of disproportionated rosin, and a metal salt of dehydrogenated rosin, and in particular, a metal salt of dehydroabithienoic acid, It is preferable to use at least one metal salt of a rosin selected from a metal salt of abithienoic acid and a metal salt of dihydropimaric acid. The above-mentioned rosin and a metal having 1 to 3 valences are usually 40 to 150 ° C.
The reaction proceeds by mixing in a solvent at a temperature of preferably about 50 to 120 ° C. to obtain a reaction mixture containing a metal salt of a rosin. The reaction rate between the rosin and the metal having 1 to 3 valences is preferably 50% or less, because the effect is high in proportion to the amount of the rosin. As the metal salts of the rosins,
For example, “Pine Crystal MK1300” sold by Arakawa Chemical Industries as a rosin sodium salt
Can also be used.

(3) Additional Components (Optional Components) In the propylene-based resin composition of the present invention, in addition to the essential components of the propylene-based polymer and the metal salt of rosin, other additional components are used in the present invention. Can be blended within a range that does not significantly impair the effect of the above. As the additional components, phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, neutralizing agents, hindered amine-based stabilizers, light stabilizers used as ordinary compounding agents for polyolefin resins, UV absorbers, lubricants, antistatic agents, metal deactivators, colorants, dispersants, peroxides, fillers, optical brighteners,
Also, resins other than the propylene-based polymer used in the present invention, ethylene-propylene-based rubber, ethylene-butene-based rubber, ethylene-hexene-based rubber, ethylene-octene-based rubber and the like can be mentioned.

Phenolic antioxidants Specific examples of the phenolic antioxidants include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3-tris ( 2-methyl-4-hydroxy-5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate], 1,3,
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, 3,9
-Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1
-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-tris (4
-T-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid;

Phosphorous antioxidants Specific examples of the phosphorus antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite,
4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,
1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t
-Butylphenyl) -4,4'-biphenylene-di-phosphonite, tetrakis (2,4-di-t-butyl-5)
-Methylphenyl) -4,4'-biphenylene-di-phosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, and the like.

[0033] Specific examples of the sulfur-based antioxidant the sulfur antioxidant include di - stearyl - thio - di - propionate, di - myristyl - thio - di - propionate, pentaerythritol - tetrakis - (3-lauryl - Thio-propionate) and the like.

[0034] Specific examples of the neutralizing agent the neutralizing agent include calcium stearate, zinc stearate, hydrotalcite, a Mizukarakku (manufactured by Mizusawa Chemical Co., Ltd.).

Hindered amine stabilizer Examples of the above hindered amine stabilizer include polycondensation of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine. , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-) Piperidyl) sebacate, N, N-bis (3-aminopropyl) ethylenediamine · 2,4-
Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,
3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [$ 6
-(1,1,3,3-tetramethylbutyl) imino-
1,3,5-triazine-2,4-diyl {(2,
2,6,6-tetramethyl-4-piperidyl) imino}
Hexamethylene ｛(2,2,6,6-tetramethyl-4
-Piperidyl) imino}], poly [(6-morpholino-
s-Triazine-2,4-diyl) [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]].

[0036] Specific examples of the lubricants slipping agents, oleamide, stearamide, behenic acid amide, higher fatty acid amides such as ethylene bis-stearic Lloyd, silicone oil, mention may be made of higher fatty acid esters and the like.

[0037] Specific examples of the antistatic agent of the antistatic agent include higher fatty acid glycerol ester, alkyl diethanol amine, alkyl diethanol amides, alkyl diethanol amides fatty acid monoester or the like.

[II] Compounding ratio It is important that the composition ratio of each component of the propylene-based resin composition of the present invention is as shown below. The metal salt of rosin is used in an amount of 0.03 to 100 parts by weight of the propylene resin.
To 2 parts by weight, preferably 0.05 to 1 part by weight, particularly preferably 0.03 to 0.8 part by weight. When the amount of the rosin metal salt is less than the above range, the effect of improving the transparency is not sufficient, and when the amount exceeds the above range, the transparency is deteriorated as well as uneconomical.

[III] Production of propylene-based resin composition (1) Blending, melting and kneading In order to produce the propylene-based resin composition of the present invention, generally, the above components are blended in the above composition ratio. ,mixture,
It can be manufactured by melting and kneading. The mixing, melting, and kneading can be usually performed by a Henschel mixer, a super mixer, a V blender, a tumbler mixer, a ribbon blender, a Banbury mixer, a kneader blender, a single or twin screw kneading extruder, and the like. Among them, it is preferable to carry out mixing or melt-kneading with a single-screw or twin-screw kneading extruder. At this time,
A so-called masterbatch method in which a propylene-based resin is mixed with a metal salt of the above-mentioned rosin in an amount larger than a target amount in advance and then used for molding while diluting the metal salt with the propylene-based resin may be employed.

[IV] Applications The propylene-based resin composition of the present invention can obtain a desired molded article by various molding methods. Specific examples include injection molding, extrusion molding, and blow molding. Examples of the use of the injection molded product include thin food containers such as pudding, jelly, and egg tofu; tableware for food preservation and microwave cooking; storage containers for clothing and daily necessities; floppy disks, optical disks, video tapes, and the like. Cases of 8 mm video, cassette tape, etc .; Foods, cosmetics, detergents, chemicals such as insecticides, caps for various sprays, etc .; Stationery, accessories, toys; Syringes, centrifuge tubes, vials, beakers, flasks, pharmaceutical containers, etc. And molded articles for use in medical treatment. Preferred injection-molded articles include storage containers (clothes boxes) for medical and daily necessities, food containers, tableware, and the like.

[0041]

The present invention will be described more specifically with reference to the following examples and comparative examples. [I] Production of propylene-based resin <Production Example 1> [(r) -dimethylsilylenebis (2-methyl-4,5
-Benzoindenyl) zirconium chloride synthesis] O
rganometallics 1994,13,96
No. 4 was synthesized by the method described in the literature. [Synthesis of catalyst] MAO on Si manufactured by WITCO was placed in a glass reactor having an inner volume of 0.5 liter and equipped with a stirring blade.
2.4 g (20.7 mmol-Al) of O ₂ were added,
50 ml of n-heptane was introduced, and 20.0 ml of a (r) -dimethylsilylenebis (2-methylbenzoindenyl) zirconium chloride solution previously diluted in toluene.
(0.0637 mmol), followed by 4.14 m of isobutylaluminum (TIBA) · n-heptane solution.
1 (3.03 mmol) was added. Then at room temperature 2
The reaction was allowed to proceed for a period of time, and propylene was further allowed to flow for prepolymerization to obtain a solid catalyst.

[Polymerization] After sufficiently replacing the inside of a 200-liter stirred autoclave with propylene, 3 g of a triethylaluminum / n-heptane solution, 45 kg of liquefied propylene and 6.5 NL of hydrogen were introduced, and the internal temperature was lowered to 4%.
Maintained at 0 ° C. Subsequently, 1.3 g of a solid catalyst (as an amount excluding a polymer component by prepolymerization) was added. Thereafter, the temperature was raised to 65 ° C. to start polymerization, and the temperature was maintained for 3 hours. Then, 100 ml of ethanol was added to stop the reaction. Residual gas was purged and the polymer was dried. As a result, 13.1 kg of polypropylene having an MFR of 11 g / 10 minutes was obtained. As a result of analyzing this polymer, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was Mw / Mn = 2.30. Further, the average elution temperature (T ₅₀ ) measured by the following temperature rise elution fractionation (TREF) was 96.5 ° C., and the elution dispersity (σ) was 5.6.

Measurement of temperature rise elution fractionation (TREF) The peak of the elution curve by the temperature rise elution fractionation (TREF) is measured by completely dissolving the polymer once at a high temperature, then cooling, and thinly coating the surface of the inert carrier. A polymer layer was formed, and then the temperature was continuously or stepwise raised to collect the eluted components, the concentration was continuously detected, and the measurement was performed by measuring the amount and temperature of the elution. . The measurement of the elution curve was performed under the following measurement conditions. Solvent: o-dichlorobenzene Measurement concentration: 4 mg / ml Injection amount: 0.5 ml Column: 4.6 mmφ × 150 mm Cooling rate: 100 ° C. × 120 minutes

<Production Example 2> 1.0 g of a solid catalyst (as an amount excluding a polymer component by prepolymerization) and 1 g of hydrogen
Polymerization was carried out in the same manner as in <Production Example 1> except that 7.0 NL and an amount of ethylene gas of 0.45 kg were introduced into the polymerization tank. As a result, 23.0 kg of a propylene / ethylene random copolymer having an MFR of 26 g / 10 min and an ethylene content of 0.9% by weight was obtained. As a result of analyzing this polymer, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was Mw / Mn = 2.38. The average dissolution temperature (T ₅₀ ) by TREF is 89
° C, and the elution dispersity (σ) was 6.2.

<Production Example 3> Polymerization was carried out in the same manner as in <Production Example 1> except that 1.2 g of the solid catalyst, 14 NL of hydrogen and 0.95 kg of ethylene gas were introduced into the polymerization tank. . As a result, 18.1 kg of a propylene / ethylene random copolymer having an MFR of 31 g / 10 min and an ethylene content of 2.0% by weight was obtained. As a result of analyzing this polymer, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was Mw / Mn = 2.31. The average elution temperature (T ₅₀ ) by TREF is 8
The temperature was 5.2 ° C., and the elution dispersity (σ) was 6.5.

<Production Example 4 (Comparative Example)> After sufficiently replacing the inside of a 200-liter stirred autoclave with propylene, 60 l of purified n-heptane was introduced, and 40 g of diethylaluminum chloride, manufactured by Marubeni Solvay Co., Ltd. 7.5 g of titanium trichloride catalyst were introduced at 55 ° C. under a propylene atmosphere. Further, the hydrogen concentration in the gas phase is adjusted to 7.0.
Propylene at a temperature of 60 ° C. while maintaining the volume%.
After feeding 8 kg / hour and ethylene at a feed rate of 0.3 kg / hour for 4 hours, polymerization was continued for another hour. Thereafter, the product is filtered and dried,
0.2 kg of a powdery propylene / ethylene random copolymer was obtained. The MFR of this copolymer is 12 g / 10 minutes,
The ethylene content was 2.6% by weight. As a result of analyzing this copolymer, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was Mw / Mn = 4.8.
The average elution temperature (T ₅₀ ) by TREF is 97.0.
And the elution dispersity (σ) was 24.0.

[II] Production of propylene-based resin composition Example 1 0.05 parts by weight of calcium stearate as a neutralizing agent and dehydroabietic acid as a metal salt of a rosin with respect to the homopolymer of the above <Production Example 1> And tetrahydroabietic acid (dehydro / tetrahydro: 0.84 /
0.46 parts by weight of sodium and potassium salts of rosins (Na / K: 0.85 / 2.2 [weight ratio]) consisting of 0.16 [molar ratio]) and pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 part by weight.
The mixture was mixed with a supermixer for 3 minutes, melted and kneaded with an extruder having a screw diameter of 30 mm heated to 230 ° C. to prepare a pellet-shaped composition. This composition was heated at a mold temperature of 40 ° C. and a cylinder set temperature of 240 ° C.
Into an injection molding machine heated to 120 mm x 80 mm x
An injection sheet having a thickness of 2 mm was molded to prepare a test piece for evaluation.

[0048] Evaluation evaluation was measured in accordance with the following methods. Table 1 shows the results. (a) MFR: JIS-K7210 (b) Flexural modulus: JIS-K7203 (c) Transparency: Haze was measured according to JIS-K7105. (d) Odor: About 80 g of the sample pellets are placed in a clean odor-free jar, put in a gear oven controlled at 80 ° C., and heated for 2 hours. After heating 10
The test for odor was performed within minutes, and the odor was judged according to the following criteria. Odor criterion ：: No odor Δ: Slight odor is felt. X: A considerable smell is felt.

Example 2 Evaluation was made in the same manner as in Example 1 except that the propylene / ethylene random copolymer of Production Example 2 was used instead of the polypropylene homopolymer of Example 1. Table 1 shows the results.

Example 3 Evaluation was carried out in the same manner as in Example 1 except that the polypropylene homopolymer of Example 1 was replaced with the propylene / ethylene random copolymer of Production Example 3. Table 1 shows the results.

Example 4 The pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] was changed to a polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, and evaluated in the same manner as in Example 1. did. Table 1 shows the results.

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the polypropylene homopolymer of Example 1 was changed to the propylene / ethylene random copolymer produced in Production Example 4. Table 2 shows the results.

Comparative Example 2 Evaluation was made in the same manner as in Example 1 except that the metal salt of rosin added in Example 1 was not added. Table 2 shows the results.
Shown in

Comparative Example 3 The metal salt of rosin added in Example 1 was changed to sodium 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, and the amount added was 0.2. Evaluation was performed in the same manner as in Example 1 except that the amount was changed to parts by weight. Table 2 shows the results.

Comparative Example 4 Evaluation was made in the same manner as in Example 1 except that the metal salt of rosins added in Example 1 was changed to talc, and the added amount was changed to 0.2 parts by weight. Table 2 shows the results.

Comparative Example 5 Evaluation was made in the same manner as in Example 2 except that the metal salt of rosin added in Example 2 was not added. Table 3 shows the results.
Shown in

Comparative Example 6 The metal salts of rosins added in Example 2 were 1,3,2
Evaluation was performed in the same manner as in Example 1 except that 4-di (p-methylbenzylidene) sorbitol (manufactured by Nippon Rika Co., Ltd .: Gelol MD) was used, and the amount of addition was changed to 0.2 part by weight. Table 3 shows the results.

Comparative Example 7 The metal salt of a rosin used in Example 1 was changed to sodium 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, and the amount of addition was changed. Evaluation was performed in the same manner as in Example 1 except that the amount was changed to 0.2 parts by weight. Table 3 shows the results.

Comparative Example 8 The metal salt of a rosin used in Example 2 was replaced with hydroxy-
Evaluation was made in the same manner as in Example 1 except that aluminum was changed to di (t-butylbenzoic acid) and the addition amount was changed to 0.2 parts by weight. Table 3 shows the results.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

Nucleating agent A: metal salt of rosin [dehydroabietic acid and tetrahydroabietic acid ｛dehydro /
Sodium and potassium salts of rosins composed of tetrahydro: 0.84 / 0.16 (molar ratio) {Na / K:
0.85 / 2.2 (weight ratio)] Nucleating agent B: 2,2'-methylene-bis (4,6-di-t
-Butylphenyl) sodium phosphate (manufactured by Asahi Denka Co., Ltd .: NA
11) Nucleating agent C: Talc (manufactured by Maruo Calcium Co., Ltd .: MT6B) Nucleating agent D: 1,3,2,4-di (p-methylbenzylidene) sorbitol (manufactured by Nippon Rika Co., Ltd .: Gerol MD) Nucleating agent E: hydroxy -Aluminum di (t-butylbenzoate) (PTBBA-Al, manufactured by Shell Chemical Company)

[0064]

As described above, the propylene-based resin composition of the present invention is a propylene-based resin having specific physical properties polymerized using a metallocene catalyst, rather than a propylene-based resin polymerized using a conventional Ziegler-type catalyst. The use of rosin metal salt can effectively exert the effect as a nucleating agent, as a result, the flexural modulus, transparency,
Excellent odor balance.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 93:04) (72) Inventor Tatsuo Kobayashi 1 Tohocho, Yokkaichi-shi, Mie Japan Yokkaichi Technical Center, Japan

Claims (1)

[Claims] A rosin metal salt is added to 100 parts by weight of a propylene polymer having the following physical properties (a) to (c).
A propylene-based resin composition characterized by being mixed with 03 to 2 parts by weight. Physical property (a): 100 structural units obtained from propylene
~ 90 mol%, ethylene and / or α having 4 to 20 carbon atoms
-The structural unit obtained from the olefin is a propylene-based polymer having 0 to 10 mol% Physical properties (b): The molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4 Physical properties (c): The average dissolution temperature (T ₅₀ ) is in the range of 75 to 120 ° C., and the dissolution degree (σ) is 9 or less.