JP2020050857A - Manufacturing method of propylene-based resin molded body - Google Patents

Abstract

To provide a manufacturing method of a propylene-based resin molded body capable of obtaining a molded body while maintaining good antistatic performance under high temperature low humidity environment without loosing physical properties of a propylene-based resin composition and without adding complicated processes.SOLUTION: There is provided a manufacturing method of a propylene-based resin molded body for providing a molded body through a manufacturing process using a propylene-based resin composition containing a donor-acceptor antistatic agent (A) consisting of at least one kind of a semi-polar organic compound having 1 atom group represented by the following formula (4) and minimum 1 linear hydrocarbon group having 5 to 28 carbon atoms in a molecule, and at least one kind of a basic organic compound having 1 basic nitrogen atom group and minimum 1 linear hydrocarbon group having 5 to 28 carbon atoms in a molecule of 0.01 to 3 pts.wt. based on 100 pts.wt. of a propylene polymer, under atmosphere of a temperature of 60 to 160°C.SELECTED DRAWING: None

Description

  The present invention particularly relates to a method for producing a propylene-based resin molded article under a high-temperature and low-humidity environment. Specifically, under a high-temperature and low-humidity environment, a propylene-based resin composition containing an antistatic agent having a specific structure with respect to a propylene-based polymer is used. The present invention relates to a method for producing a propylene-based resin molded article capable of obtaining a molded article while maintaining good fluidity without adhering.

  BACKGROUND ART Propylene resins are widely used in various applications such as various industrial materials, various containers, daily necessities, films, and fibers because of their excellent heat resistance, moldability, transparency, and chemical resistance.

In recent years, molded articles have been obtained by various production methods using a propylene-based resin. Among them, there are many opportunities to carry out molding using fine powders such as propylene-based resin powder, pellets, and propylene-based resin particles in a high-temperature and low-humidity environment. For example, when using a propylene-based resin pellet containing a filler such as talc, in order to remove water easily contained in the filler, drying at about 80 to 100 ° C. before molding is generally performed. . In addition, when propylene-based resin particles are used as a raw material in the powder slush method or the like, a high-temperature and low-humidity environment is formed inside the molding device. Further, in order to improve the quality of the molded body such as physical properties and dimensional accuracy, annealing (heat treatment) of the molded body at about 80 to 120 ° C. is generally performed.
In those cases, the propylene-based resin is an insulating material, so it is charged and adheres to the feeder, hopper, piping, and the inside of the molding equipment during molding, causing clogging and contamination or deteriorating the yield, Improvement is required.

Generally, addition of an antistatic agent is known as a technique for preventing charging of a propylene-based resin (for example, see Non-Patent Document 1). However, preferably used antistatic agents such as glycerin monoester, alcohol, alkylamine, etc., exhibit an antistatic function by a mechanism of expressing conductivity by absorbing moisture after transferring from the inside of the resin to the surface, There is a problem that it does not function sufficiently in a high temperature and low humidity environment. Further, a polyether / polyolefin block copolymer-based antistatic agent is also commercially available as a polymer-type antistatic agent which does not depend on moisture (for example, see Patent Document 1). It is necessary to add more than parts by weight, and there have been problems such as a decrease in elastic modulus, a deterioration in hue, and an increase in cost.
As the polymer type antistatic agent, boron-based compounds other than the above are known. Patent Literature 2 discloses a foam molded article that exhibits an antistatic effect even in a low-humidity environment by applying and spraying a boron-based compound. However, this method has a problem that the time and cost required for production increase because the steps of coating, spraying and drying increase.

Japanese Patent No. 5681419 JP 2014-193949 A

Polypropylene Handbook Co., Ltd. Industrial Research Institute, published in 1998

  An object of the present invention is to form the propylene-based resin composition while maintaining good antistatic performance under a high-temperature and low-humidity environment without impairing the physical properties of the propylene-based resin composition, and without adding complicated steps, in the state of the prior art. An object of the present invention is to provide a method for producing a propylene-based resin molded article from which a molded article can be obtained.

The present inventors have conducted intensive studies in order to solve the above-described problems, and by adding a specific antistatic agent to the propylene-based polymer at a predetermined ratio, without impairing the physical properties of the propylene-based resin composition, and The present inventors have found a method for producing a propylene-based resin molded article that can obtain a molded article while maintaining good antistatic performance under a high-temperature and low-humidity environment without adding complicated steps, and have completed the present invention.
That is, the present invention provides the following method for producing a propylene-based resin molded article.

[1] At least one atomic group represented by the following formula (1) and a straight-chain hydrocarbon group having 5 to 28 carbon atoms in the molecule are contained in 100 parts by weight of the propylene-based polymer (a). And at least one basic organic compound having at least one basic nitrogen atom group and at least one straight-chain hydrocarbon group having 5 to 28 carbon atoms in the molecule. Using a propylene-based resin composition containing 0.01 to 3 parts by weight of a donor-acceptor-based antistatic agent (A) consisting of A method for producing a propylene-based resin molded article, characterized in that it is obtained.

[2] The propylene-based resin molded article according to [1], wherein the donor-acceptor antistatic agent (A) is a compound represented by the following formula (2) or a compound represented by the following formula (3). Production method.

(Wherein, R ¹ and R ² are each independently R ⁷ CO—OCH ₂ — or HOCH ₂ —, and at least one is R ⁷ CO—OCH ₂ —; and R ³ and R ⁴ are Each independently is CH ₃ —, C ₂ H ₅ —, HOCH ₂ —, HOC ₂ H ₄ — or HOCH ₂ CH (CH ₃ ) —, and R ⁵ is —C ₂ H ₄ — or —C ₃ H _6- , and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbons.)

(Wherein, R ¹ and R ² are each independently R ⁷ CO—OCH ₂ — or HOCH ₂ —, and at least one is R ⁷ CO—OCH ₂ —; and R ³ and R ⁴ are Each independently is CH ₃ —, C ₂ H ₅ —, HOCH ₂ —, HOC ₂ H ₄ — or HOCH ₂ CH (CH ₃ ) —, and R ⁵ is —C ₂ H ₄ — or —C ₃ H _6- , and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbons.)

[3] The method for producing a propylene-based resin molded article according to [1] or [2], wherein the molded article is obtained through a production process in an atmosphere having a relative humidity of 0 to 30%.

[4] The method for producing a propylene-based resin molded article according to any one of [1] to [3], wherein the molded article is obtained through a production process in an atmosphere at a temperature of 70 to 120 ° C.

  The method for producing a propylene-based resin molded article of the present invention is a method for molding while maintaining good antistatic performance under a high-temperature and low-humidity environment without impairing the physical properties of the propylene-based resin composition, and without adding complicated steps. Very useful because you can get the body.

  The method for producing a propylene-based resin molded product according to the present invention is directed to a propylene-based resin comprising a donor-acceptor antistatic agent (A) in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of a propylene-based polymer (a). It is characterized in that a molded product is obtained through a manufacturing process using a resin composition in an atmosphere at a temperature of 60 to 160 ° C.

Hereinafter, the propylene-based resin composition, the method for producing the propylene-based resin composition, and the method for producing the propylene-based resin molded article according to the present invention will be described in detail.
[1] Component constituting propylene resin composition (1) Propylene polymer (a)

(I) Melt flow rate (MFR) of propylene polymer (a)
The MFR of the propylene-based polymer (a) used in the present invention is not particularly limited, but the lower limit of the melt flow rate (MFR) in accordance with JIS K7210 (230 ° C., 2.16 kg load) is preferably 0.1 g / 10. Min, more preferably 0.2 g / 10 min, even more preferably 0.3 g / 10 min. The upper limit is preferably 500 g / 10 minutes, more preferably 300 g / 10 minutes, and even more preferably 100 g / 10 minutes. When the melt flow rate (MFR) is equal to or more than the lower limit, the moldability can be improved and a satisfactory product can be obtained. Further, when the content is equal to or less than the upper limit, the mechanical strength is improved.
Melt flow rate (MFR) is to control the temperature and pressure, which are the polymerization conditions for the propylene-based polymer (a), and to control the amount of hydrogen added in the method of adding a chain transfer agent such as hydrogen during polymerization. Thereby, the adjustment can be easily performed.

(Ii) Structure of Propylene-Based Polymer (a) The propylene-based polymer (a) used in the propylene-based resin composition of the present invention is not particularly limited, but includes propylene homopolymer, propylene and α-olefin. Propylene-based random copolymers, propylene-based block copolymers composed of propylene and α-olefins, and mixtures thereof.
The propylene polymer (a) is preferably a homopolymer from the viewpoint of rigidity, a random copolymer of propylene and an α-olefin from the viewpoint of transparency and impact resistance, and propylene from the viewpoint of impact resistance. And a block copolymer composed of α-olefin. Examples of the α-olefin used for the copolymerization include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, 1-butene, 1-hexene, and 1-octene. One or two or more α-olefins copolymerized with propylene may be used. Of these, ethylene and 1-butene are preferred. Ethylene is more preferred. These propylene polymers may be used as a mixture of two or more kinds.

(Iii) Catalyst of propylene-based polymer (a) In the propylene-based polymer (a) used in the present invention, the catalyst used for producing the propylene-based polymer (a) is not particularly limited, It is preferable to use a stereoregular catalyst. Examples of the stereoregular catalyst include a Ziegler catalyst and a metallocene catalyst.

  Ziegler catalysts include titanium halides such as titanium trichloride, titanium tetrachloride, and trichloroethoxy titanium; transition metal components such as a contact product of the titanium halide and a magnesium compound represented by magnesium halide; and alkyl aluminum. Compounds or two-component catalysts thereof with organometallic components such as halides, hydrides, alkoxides and the like, and further added with electron-donating compounds containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. Component catalysts are exemplified.

As the metallocene catalyst, a supported type is preferred.
A particularly preferred example of the supported metallocene catalyst is an ion-exchange layered silicate in which a carrier also functions as a promoter. Specifically, it is obtained by combining component [A], component [B] described below, and component [C] added as needed.

-Component [A] metallocene complex Transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand-Component [B] Promoter ion-exchangeable layered silicate-Component [C] organoaluminum Compound

Component [A] Metallocene Complex As the component [A], specifically, a compound represented by the following formula [I] can be used.
^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b) MXY ··· [I]
In the formula [I], Q represents a binding group bridging two conjugated five-membered ring ligands.
M represents a transition metal belonging to Groups 4 to 6 of the periodic table, and among them, titanium, zirconium, and hafnium are preferable.
X and Y are each independently hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, And 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 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen, a hydrocarbon group containing 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, And a hydrocarbon group containing nitrogen, a hydrocarbon group containing nitrogen or a hydrocarbon group containing boron. Further, two adjacent R ¹ or two R ² may be bonded to each other to form a C _{4 to} C ₁₀ ring. In particular, it is preferable to form a 6-membered ring or a 7-membered ring to form an indene ring and an azulene ring together with the conjugated 5-membered ring.
a and b are integers satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4.
Examples of the bonding group Q that bridges between two conjugated five-membered ring ligands include an alkylene group, an alkylidene group, a silylene group, and a germylene group. These may be those in which a hydrogen atom is substituted by an alkyl group, halogen, or the like. Particularly, a silylene group is preferable.

Specific examples of the metallocene complex include the following compounds.
(1) methylene bis (cyclopentadienyl) zirconium dichloride (2) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride (3) isopropylidene (cyclopentadienyl) (3,4 -Dimethylcyclopentadienyl) zirconium dichloride (4) ethylene (cyclopentadienyl) (3,5-dimethylpentadienyl) zirconium dichloride (5) methylenebis (indenyl) zirconium dichloride (6) ethylenebis (2-methylind Nil) zirconium dichloride (7) ethylene 1,2-bis (4-phenylindenyl) zirconium dichloride (8) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride

(9) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride (10) dimethylsilylenebis (indenyl) zirconium dichloride (11) dimethylsilylenebis (4,5,6,7-tetrahydroindenyl ) Zirconium dichloride (12) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (13) dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride (14) methylphenylsilylene bis [1- ( 2-methyl-4,5-benzo (indenyl)] zirconium dichloride (15) dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride (16) dimethylsyl Lenbis [1- (2-methyl-4H-azulenyl)] zirconium dichloride (17) dimethylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride (18) dimethylsilylene Bis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride (19) dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azulenyl)] zirconium dichloride

(20) diphenylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride (21) dimethylsilylenebis [1- (2-methyl-4- (phenylindenyl) )] Zirconium dichloride (22) dimethylsilylenebis [1- (2-ethyl-4- (phenylindenyl))] zirconium dichloride (23) dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azulenyl) )] Zirconium dichloride (24) dimethylgermylene bis (indenyl) zirconium dichloride (25) dimethylgermylene (cyclopentadienyl) (fluorenyl) zirconium dichloride Also, other fourth, fifth and sixth compounds such as titanium compounds and hafnium compounds Group transition metal compounds Preferred are the same compounds as described above. These compounds may be used in combination for the catalyst component and catalyst for producing the propylene-based polymer (a) used in the present invention.

・ Component [B] Co-catalyst (ion-exchange layered silicate)
The ion-exchangeable layered silicate is not limited to a natural product, and may be an artificially synthesized product. A clay compound can be used as the ion-exchange layered silicate. Specific examples of the clay compound include, for example, the following described in “Clay Mineralogy” by Haruo Shiramizu, Asakura Shoten (1995) Layered silicates are mentioned.
(A) Kaolin family such as dickite, nacrite, kaolinite, anoxite, metahaloysite, halloysite, etc., whose main constituent layer is a 1: 1 type structure, and serpentine family such as chrysotile, lizardite, antigolite, etc. Smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculites such as vermiculite, mica, illite, sericite, and chlorite whose 2: 1 type structure is the main constituent layer Mica, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite

The silicate used in the present invention may be a layered silicate in which a mixed layer of the above (A) and (A) is formed.
In the present invention, the silicate as a main component is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite.

The activity can be improved by chemically treating these silicates with acids, salts, alkalis, oxidizing agents, reducing agents, organic solvents and the like.
The acid treatment removes impurities on the surface of the ion-exchanged layered silicate particles, or exchanges interlayer cations, and may elute some or all of cations such as Al, Fe, and Mg in the crystal structure. it can.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, and sulfuric acid, and are preferably inorganic acids, and particularly preferably sulfuric acid.
The acid treatment conditions are not particularly limited, but are preferably such conditions that an aqueous solution of an acid of 5 to 50% by weight is reacted at a temperature of 60 to 100 ° C. for 1 to 24 hours, and the acid concentration is changed during the reaction. You may. After the acid treatment, washing is usually performed. Washing is an operation of separating and removing the acid contained in the treatment system from the ion-exchange layered silicate.

It is preferable to select and use a salt containing a specific cation as the salt used in the salt treatment. As the kind of the cation, a monovalent to tetravalent metal cation is preferable, and a cation of Li, Ni, Zn, or Hf is particularly preferable.
The following can be exemplified as specific salts.
The cations with Li include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), Li (ClO ₄ ), Li ₂ (C ₂ O ₄ ), LiNO ₃ , Li (OOCCH ₃ ), and Li. ₂ (C ₄ H ₄ O ₄ ) and the like.
Examples of those whose cation is Ni include NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
When the cation is Zn, Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , Examples include ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , and ZnI ₂ .
As those cations of _{Hf, Hf (OOCCH 3) 4} , Hf (CO 3) 2, Hf (NO 3) 4, Hf (SO 4) 2, HfOCl 2, HfF 4, HfCl 4, HfBr 4, HfI _{4 and the} like.

  After the chemical treatment, drying is performed. Generally, the drying can be performed at a drying temperature of 100 to 800 ° C. Not preferred. Since the characteristics change depending on the drying temperature even if the structure is not destroyed, it is preferable to change the drying temperature according to the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is dry air, dry nitrogen, dry argon, or under reduced pressure. The drying method is not particularly limited, and can be carried out by various methods.

-Component [C] Organoaluminum Compound The organoaluminum compound of the component [C] is a component optionally used as needed, and a compound represented by the following formula [II] is optimal.
^{_{(AlR 4 p X 3-p}} ) q ··· [II]
In the formula [II], R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p is an integer of 1-3 and q is an integer of 1-2.
R ⁴ is preferably an alkyl group, and X is preferably an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and an amino group having 1 to 8 carbon atoms when X is an amino group.
Of these, a trialkylaluminum of p = 3 and q = 1 and a dialkylaluminum hydride of p = 2 and q = 1 are preferred. More preferably, R ⁴ is a trialkyl aluminum having 1 to 8 carbon atoms.

  The organoaluminum compounds can be used alone or in combination of two or more or in combination. Further, the organoaluminum compound can be added and used not only at the time of preparing the catalyst but also at the time of preliminary polymerization or main polymerization.

(Iv) Method for producing propylene-based polymer (a) The method for producing propylene-based polymer (a) is not particularly limited, but a polymerization method using the above stereoregular catalyst is preferred. Examples of the stereoregular catalyst include a Ziegler catalyst and a metallocene catalyst. A Ziegler-based propylene-based polymer can be produced by homopolymerizing propylene or copolymerizing propylene with an α-olefin using a Ziegler catalyst. A metallocene-based propylene-based polymer can be produced by homopolymerizing propylene or copolymerizing propylene with an α-olefin using a metallocene catalyst. It is more preferable to use a metallocene catalyst because a propylene-based polymer having low volatility can be obtained.

The method for producing the propylene-based polymer (a) includes, in the presence of the above catalyst, a slurry polymerization method using an inert solvent, a solution polymerization method, a gas phase polymerization method using substantially no solvent, And a polymerization method such as a bulk polymerization method.
For example, in the case of the slurry polymerization method, the reaction can be carried out in an inert hydrocarbon such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene and xylene. In the case of a bulk polymerization method, it can be carried out in a liquid polymerization monomer. The polymerization temperature is usually from -80 to 150C, preferably from 40 to 120C. The polymerization pressure is preferably 1 to 60 atm (0.10 to 6.08 MPa), and the molecular weight of the obtained propylene-based polymer (a) can be adjusted with hydrogen or another known molecular weight regulator. . The polymerization is carried out by a continuous or batch-type reaction, and the condition may be a commonly used condition. Further, the polymerization reaction may be performed in one stage or may be performed in multiple stages.
When a metallocene catalyst is used, it is desirable to perform a preliminary polymerization treatment before the main polymerization is performed. Examples of the monomer to be subjected to the prepolymerization include α-olefins such as ethylene, propylene, 1-butene, and 1-hexene; diene compounds such as 1,3-butadiene; and vinyl compounds such as styrene and divinylbenzene. .
This prepolymerization is preferably carried out under mild conditions in an inert solvent, and is preferably 0.01 to 1,000 g, preferably 0.1 g, per 1 g of the solid catalyst (total of the components [A] and [B]). It is desirable to carry out so as to produce ~ 100 g of polymer.

  The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene and cyclohexane, or a liquefied α-olefin. In the present invention, it is desirable to increase the amount of polymer produced per solid catalyst (when the solid catalyst is preliminarily polymerized, does not include the polymer produced by the prepolymerization) as much as possible. In order to increase the amount of polymer produced, it is desirable to set both the polymerization temperature and the polymerization pressure to be higher.

Usually, the polymerization temperature is selected from 60 to 90 ° C., and the polymerization pressure is selected from about 1.5 to 4 MPa. In particular, in the case of the bulk polymerization method, the polymerization temperature is preferably from 60 to 80 ° C., and the polymerization pressure is preferably selected from about 2.5 to 4 MPa in correlation with the temperature. On the other hand, in the case of the gas phase polymerization method, the polymerization temperature is preferably 70 to 90 ° C., and is preferably selected from about 1.5 to 4 MPa.
Further, by increasing the residence time of the solid catalyst, it is possible to increase the amount of polymer produced per solid catalyst, but if it is too long, the productivity is affected. Preferred residence times are 1 to 8 hours, more preferably 1 to 6 hours. The polymerization conditions are desirably set so that the amount of polymer produced per gram of the solid catalyst including the carrier is 20 kg or more, preferably 25 kg or more, and more preferably 30 kg or more.
Further, hydrogen may be present as a molecular weight regulator in the polymerization system. Further, the polymerization may be carried out in multiple stages by changing the polymerization temperature, the concentration of the molecular weight regulator and the like.

In the present invention, after the polymerization is completed, the obtained propylene-based polymer (a) is more preferably prepared using an inert saturated hydrocarbon solvent such as propane, butane, pentane, hexane, or heptane, or a liquid α-olefin. May be washed using an inert hydrocarbon solvent having 3 or 4 carbon atoms or a liquid α-olefin.
The washing method is not particularly limited, and a known method such as decantation of the supernatant after contact treatment in a stirring tank, countercurrent washing, and separation from a washing solution by a cyclone can be used.
Further, a deactivator may be added before or simultaneously with the washing. There is no particular limitation on the quenching agent, and water, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone and methyl ethyl ketone, and mixtures thereof can be used.

(V) Molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) of propylene-based polymer (a)
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the propylene polymer (a) used in the present invention obtained by gel permeation chromatography (GPC) measurement is preferably 1.5 to 4.0. preferable.
The lower limit of the molecular weight distribution is preferably 2.0 or more, more preferably 2.5 or more, and the upper limit is preferably 3.8 or less, more preferably 3.5 or less.
When the lower limit of the molecular weight distribution is not less than a certain value, the range of conditions for production and purification of the propylene-based polymer (a) is widened, so that the production efficiency is improved, which is preferable. In addition, when the upper limit is less than a certain value, it indicates that the lengths of the molecular chains are very uniform, and unreacted monomers, dimers, low-molecular-weight compounds, and amorphous components that are considered to cause the generation of volatile components It is preferable because the content of relatively low molecular weight components such as oligomers and the like is reduced.

  The weight average molecular weight (Mw) of the propylene polymer (a) used in the present invention is preferably in the range of 100,000 to 600,000. If the weight average molecular weight Mw is 600,000 or less, molding becomes easy. On the other hand, when the weight average molecular weight Mw is 100,000 or more, low crystal components are reduced, mold contamination, bleed-out, solvent elution, and the like are suppressed, and the impact resistance of the molded product is improved, which is practical.

(2) Donor-acceptor antistatic agent (A)
A semipolar organic compound having one atomic group represented by the following formula (1) and at least one linear hydrocarbon group having 5 to 28 carbon atoms in a molecule (hereinafter, referred to as a semipolar organic compound) And a basic organic compound having at least one basic nitrogen atom group and at least one linear hydrocarbon group having 5 to 28 carbon atoms in the molecule (hereinafter referred to as a basic organic compound). A donor-acceptor antistatic agent comprising a composition obtained by uniformly mixing at least one kind with a donor / acceptor system.

  This differs from the conventionally used antistatic agents in that both the donor compound and the acceptor compound have at least one straight-chain hydrocarbon group and are combined with the polypropylene polymer matrix in a multiple manner with van der Waals. By applying a force, a Coulomb force-expressing portion having an antistatic effect is stably present for a long period of time. Although donor-acceptor hybrid type compounds based on electron conduction have been known for a long time, they have completely different mechanisms and structures from the donor-acceptor antistatic agent used in the present invention.

  The semipolar organic compound preferably used in the present invention refers to a borane with respect to the adjacent hydroxyl group where the ester between the polyhydric alcohol and the linear fatty acid where the adjacent hydroxy group remains remains. An acid or a lower alcohol borate ester is reacted, or a straight chain hydrocarbon compound having an adjacent hydroxy group is reacted with a boric acid or a lower alcohol borate ester. Is obtained by reacting a straight-chain fatty acid with a hydroxy group remaining after reacting a polyhydric alcohol having a valency of at least 3 with boric acid or a boric acid ester of a lower alcohol. What is obtained is a solid having a strong van der Waals force.

  Preferred examples of the polyhydric alcohol or the partial fatty acid ester of the polyhydric alcohol used for the semipolar organic compound (borate complex) in the present invention include polyglycerin such as glycerin, diglycerin, triglycerin, and tetraglycerin; 14-24 1,2-alkanediol, sorbitol, sorbitan, sucrose, pentaerythritol, dipentaerythritol, polypentaerythritol such as tripentaerythritol, trimethylolethane, trimethylolpropane, polyoxyethylene glycerin, polyoxyethylene Polyhydric alcohols such as sorbitan, glycerin higher fatty acid monoester, diglycerin higher fatty acid monoester, triglycerin higher fatty acid monoester, tetraglycerin higher fatty acid monoester Polyglycerin higher fatty acid monoester, sorbitol higher fatty acid monoester, sorbitan higher fatty acid monoester, sucrose higher fatty acid monoester, pentaerythritol higher fatty acid mono or diester, dipentaerythritol higher fatty acid mono or diester, tripentaerythritol higher fatty acid Polypentaerythritol higher fatty acid monoesters such as mono- or diesters, trimethylolethane higher fatty acid monoesters, trimethylolpropane higher fatty acid monoesters, polyoxyethylene glycerin higher fatty acid monoesters, and polyoxyethylene sorbitan higher fatty acid monoesters. Higher fatty acid partial esters of polyhydric alcohols (higher fatty acids include hexanoic acid, octanoic acid, nonanoic acid, Kang acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, oleic acid, etc. erucic acid) can be exemplified. Particularly, glycerin higher fatty acid monoester and pentaerythritol higher fatty acid monoester or diester are preferable.

  The basic organic compound preferably used in the present invention is an N-alkyl-substituted primary, secondary or tertiary amine having at least one straight-chain hydrocarbon group or a straight-chain hydrocarbon group having at least one straight-chain hydrocarbon group. Whether ethylene oxide is added to the primary and secondary amines having one and an N-hydroxyethyl substituent is bonded thereto, and further, a linear fatty acid is reacted to the terminal hydroxy group, Alternatively, a straight-chain 2-hydroxyaliphatic amine produced by reacting ammonia with an epoxidized straight-chain hydrocarbon, or a primary and secondary straight-chain 2-hydroxyaliphatic amine Ethylene oxide is added to attach an N-hydroxyethyl substituent, or such that one amino group in polyalkylene polyamine remains. The reaction is performed by reacting a polyalkylene polyamine with a straight-chain fatty acid, and all other amino groups are amidated with a fatty acid. As a characteristic, similar to the semipolar organic compound, van der Waals force Strong solid.

  Preferred examples of the basic organic compound (aliphatic amine) in the present invention include octylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, cocoamine, tallowamine, soyamine, N, N-dicocoamine, N, N-dicocoamine. N-ditaroamine, N, N-disoiamine, N-lauryl-N, N-dimethylamine, N-myristyl-N, N-dimethylamine, N-palmityl-N, N-dimethylamine, N-stearyl-N, N -Dimethylamine, N-coco-N, N-dimethylamine, N-tallow-N, N-dimethylamine, N-soy-N, N-dimethylamine, N-methyl-N, N-ditallowamine, N-methyl -N, N-dicocoamine, N-oleyl-1,3-diaminopropane, N-tallow-1,3 Diaminopropane, hexamethylenediamine, N-lauryl-N, N, N-trimethylammonium chloride, N-palmityl-N, N, N-trimethylammonium chloride, N-stearyl-N, N, N-trimethylammonium chloride, N -Docosyl-N, N, N-trimethylammonium chloride, N-coco-N, N, N-trimethylammonium chloride, N-tallow-N, N, N-trimethylammonium chloride, N-soy-N, N, N -Trimethylammonium chloride, N-lauryl-N, N-dimethyl-N-benzylammonium chloride, N-myristyl-N, N-dimethyl-N-benzylammonium chloride, N-stearyl-N, N-dimethyl-N-benzyl Ammonium chloride, N-coco-N, N-di Chill-N-benzylammonium chloride, N, N-dioleyl-N, N-dimethylammonium chloride, N, N-dicoco-N, N-dimethylammonium chloride, N, N-ditarow-N, N-dimethylammonium chloride, N, N-disoi-N, N-dimethylammonium chloride, N, N-bis (2-hydroxyethyl) -N-lauryl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N- Stearyl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-oleyl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-coco-N-methylammonium Chloride, N, N-bis (polyoxyethylene) -N-lauryl-N-methylammonium Muchloride, N, N-bis (polyoxyethylene) -N-stearyl-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-oleyl-N-methylammonium chloride, N, N-bis ( Polyoxyethylone) -N-coco-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) laurylaminobetaine, N, N-bis (2-hydroxyethyl) tridecylaminobetaine, N, N -Bis (2-hydroxyethyl) myristylaminobetaine, N, N-bis (2-hydroxyethyl) pentadecylaminobetaine, N, N-bis (2-hydroxyethyl) palmitylaminobetaine, N, N-bis ( 2-hydroxyethyl) stearylaminobetaine, N, N-bis (2-hydroxyethyl) Ilaminobetaine, N, N-bis (2-hydroxyethyl) docosylaminobetaine, N, N-bis (2-hydroxyethyl) octacosylaminobetaine, N, N-bis (2-hydroxyethyl) cocoamino Betaine, N, N-bis (2-hydroxyethyl) tallow aminobetaine,

Hexamethylenetetramine, N- (2-hydroxyethyl) laurylamine, N- (2-hydroxyethyl) tridecylamine, N- (2-hydroxyethyl) myristylamine, N- (2-hydroxyethyl) pentadecylamine, N- (2-hydroxyethyl) palmitylamine, N- (2-hydroxyethyl) stearylamine, N- (2-hydroxyethyl) oleylamine, N- (2-hydroxyethyl) docosylamine, N- (2-hydroxyethyl ) Octacosylamine, N- (2-hydroxyethyl) cocoamine, N- (2-hydroxyethyl) tallowamine, N-methyl-N- (2-hydroxyethyl) laurylamine, N-methyl-N- (2-hydroxy Ethyl) tridecylamine, N-methyl-N- (2-hydroxy Tyl) myristylamine, N-methyl-N- (2-hydroxyethyl) pentadecylamine, N-methyl-N- (2-hydroxyethyl) palmitylamine, N-methyl-N- (2-hydroxyethyl) stearyl Amine, N-methyl-N- (2-hydroxyethyl) oleylamine, N-methyl-N- (2-hydroxyethyl) docosylamine, N-methyl-N- (2-hydroxyethyl) octacosylamine, N-methyl- N- (2-hydroxyethyl) cocoamine, N-methyl-N- (2-hydroxyethyl) tallowamine, N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) triamine Decylamine, N, N-bis (2-hydroxyethyl) myristylamine, N, N-bis (2-hydroxy Ethyl) pentadecylamine, N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-hydroxyethyl) oleylamine, N-bis (2-hydroxyethyl) docosylamine, N, N-bis (2-hydroxyethyl) octakosylamine, N, N-bis (2-hydroxyethyl) cocoamine, N, N-bis (2-hydroxyethyl) N, N-bis (2-hydroxyethyl) aliphatic amines such as tallowamine, the N, N-bis (2-hydroxyethyl) aliphatic amine and lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behen Acids, mono- or diesters with fatty acids such as erucic acid, polyoxyethylene lauryl amino ether, Polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene coco amino ether, polyoxyethylene aliphatic amino ether such as polyoxyethylene tallow amino ether, and the polyoxyethylene aliphatic amino ether and the fatty acid Mono or diester,

N- (lauroyloxyethyl) -N- (stearoyloxyethoxyethyl) stearylamine, N, N, N ', N'-tetra (2-hydroxyethyl) -1,6-diaminohexane, N-lauryl-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-stearyl-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N- Coco-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-tallow-N, N', N'-tris (2-hydroxyethyl) -1,3-diamino Propane, N, N-dicoco-N ', N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N, N-ditarow-N', N'-bis (2-hydroxyethyl) -1 , 3 Diaminopropane, N-coco-N, N ', N'-tris (2-hydroxyethyl) -1,6-diaminohexane, N-tallow-N, N', N'-tris (2-hydroxyethyl)- 1,6-diaminohexane, N, N-dicoco-N ', N'-bis (2-hydroxyethyl) -1,6-diaminohexane, N, N-ditarow-N', N'-bis (2- (Hydroxyethyl) -1,6-diaminohexane, N- (2-hydroxyethyl) -2-hydroxylaurylamine, N- (2-hydroxyethyl) -2-hydroxymyristylamine, N- (2-hydroxyethyl)- 2-hydroxypalmitylamine, N- (2-hydroxyethyl) -2-hydroxystearylamine, N, N-bis (2-hydroxyethyl) -2-hydroxylauryl Min, N, N-bis (2-hydroxyethyl) -2-hydroxymyristylamine, N, N-bis (2-hydroxyethyl) -2-hydroxypalmitylamine, N, N-bis (2-hydroxyethyl) -2-hydroxystearylamine, 2,2'-bis (lauric amide) diethylamine, 2,2'-bis (myristic amide) diethylamine, 2,2'-bis (palmitic amide) diethylamine, 2,2 ' -Bis (stearic acid amide) diethylamine, N- (2- (lauric acid amide)) ethyl-N- (2 '-(stearic acid amide)) ethylamine, N- (2- (myristic acid amide)) ethyl-N -(2 '-(stearic acid amide)) ethylamine, N- (3- (lauric acid amide)) propyl-N, N-dimethylamido N- (3- (myristic amide)) propyl-N, N-dimethylamine, N- (3- (palmitic amide)) propyl-N, N-dimethylamine, N- (3- (stearic acid) Amido)) propyl-N, N-dimethylamine, N- (3- (lauroyloxy)) propyl-N, N-dimethylamine, N- (3- (myristoyloxy)) propyl-N, N-dimethylamine, N- (3- (palmitoyloxy)) propyl-N, N-dimethylamine, N- (3- (stearoyloxy)) propyl-N, N-dimethylamine, N, N-bis (3- (lauric acid amide) ) Propyl) methylamine, N, N-bis (3- (myristic amide) propyl) methylamine, N, N-bis (3- (palmitic amide) propyl) methylamine Or N, N-bis (3- (stearamide) propyl) such as methyl amine may be exemplified.

  Formulas (4) to (11) show examples of the donor-acceptor antistatic agent (A) in the present invention.

In the above formulas (4) to (11) as examples, the upper semipolar organic boron compound portion is used as a donor component, the lower tertiary amine portion is used as an acceptor component, and both are reacted at a molar ratio of about 1: 1. "Δ +" of the donor component indicates that a polarity exists in a covalent bond in the molecule, and (+) indicates that the oxygen atom has a strong electron-donating property. (-) Indicates that the boron atom has a stronger electron-withdrawing property, "→" indicates a path for attracting electrons, and "----" indicates that the interatomic bonding force is weaker. It shows the state that was done.
The donor-acceptor antistatic agent (A) is prepared by mixing and reacting a donor component and an acceptor component in a molar ratio of about 1: 1 before mixing with the propylene-based polymer (a). Preferably. If the donor component and the acceptor component are simply mixed separately with the propylene-based polymer (a) without reacting in advance, there is very little chance of the two components reacting in the mixture. , It is difficult to obtain the effects of the present invention. Also, the mixture molar ratio of the two components is preferably closer to 1: 1. If the mixture molar ratio is in the range of about 1: 0.8 to 1: 1.25, the molecular compound is sufficiently formed. This is preferable because the effects of the invention can be easily obtained.

The content of the donor-acceptor antistatic agent (A) is 0.01 to 3 parts by weight based on 100 parts by weight of the propylene-based polymer (a). When the amount is 0.01 part by weight or more, a sufficient antistatic effect and oxidation stability are obtained, and when the amount is 3 parts by weight or less, there is no concern about a boron component present near the surface of the molded body. In particular, when used for semiconductor-related components, boron and phosphorus are components used as dopants, and it is not preferable that these components exist near the surface of the molded body.
The lower limit of the content of the donor / acceptor type antistatic agent (A) is preferably 0.1 part by weight, more preferably 0.2 part by weight, further preferably 0.3 part by weight or more, and particularly preferably 0.5 part by weight or more. It is more than weight part. The upper limit of the content of the donor / acceptor antistatic agent (A) is preferably 2 parts by weight, more preferably 1 part by weight, and further preferably 0.8 part by weight.
As such a donor-acceptor antistatic agent (A), a commercially available one can be used. Specifically, Biomicel BN-105 (trade name, manufactured by Boron Research Laboratories, Inc .; compound represented by the above formula (2), mC ₄₂ H ₈₁ O ₈ B + nC ₂₃ H ₄₈ ON ₂ , see Product Safety Data Sheet) And biomicel BN-77 (compound represented by the above formula (3), mC ₄₂ H ₈₁ O ₈ B + nC ₂₃ H ₄₇ O ₂ N, see Product Safety Data Sheet).
Among the above, in the case where the production process is performed in an atmosphere at a temperature of 80 ° C. or higher, it is preferable to use biomicel BN-105 because the stability of the antistatic effect is excellent.

(3) Antioxidant The propylene-based resin composition of the present invention may further contain various phenolic antioxidants, phosphorus-based antioxidants, and thio-based antioxidants. Specifically, 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) Butane, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,3,5-trimethyl-2 Phenolic antioxidants such as 4,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Agent, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis (2,4-di-t-butyl) Phenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphite Phosphonic antioxidants such as phonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylene-di-phosphonite, di-stearyl-β, β′- Thio-di-propionate, di-myristyl-β, β′-thio-di-propionate, di-lauryl-β, β′-thio-di-propionate and other thio-based antioxidants An agent can be preferably mentioned.

  The preferred content of the phenolic antioxidant is in the range of 0.02 to 0.2 parts by weight based on 100 parts by weight of the propylene polymer (a). When the content of the phenolic antioxidant is 0.02 parts by weight or more, deterioration of the propylene-based polymer due to heat can be prevented, and an increase in the amount of volatile components can be suppressed. When the content of the phenolic antioxidant is 0.2 parts by weight or less, the generation of outgas derived from the antioxidant is suppressed, the production cost is suppressed, and the color of the product is improved, which is preferable. In addition, when the content is 0.2 parts by weight or less, direct contamination of the semiconductor contents by blooming is suppressed, and it is preferable that the content is not recognized as a volatile component.

Further, the lower limit of the content (parts by weight) of the phenolic antioxidant is preferably adjusted so as to satisfy the following formula with respect to 100 parts by weight of the propylene-based polymer (a).
3 × 10 ⁻³ B−0.67
(However, the unit is parts by weight, B is the molding temperature (° C.), and a value less than 0.02 is 0.02.)
This is because, when an electronic device component carrying case is obtained as a molded body in the injection molding method, if the case is large, thin, or has a complicated shape, it is necessary to increase the molding temperature. However, as the molding temperature is higher, thermal degradation is accelerated and volatile components increase, so that a large amount of a phenolic antioxidant is required. On the other hand, the more the phenolic antioxidant is contained, the worse the hue may be. Therefore, the content of the phenolic antioxidant represented by the above formula is most effective in consideration of the moldability, the amount of volatile components and the hue required for practical use of the product. Here, the molding temperature refers to the cylinder set temperature of the (injection) molding machine.

  Further, an amine-based antioxidant represented by the following formula (12) or (13) having good NOx gas discoloration resistance, 5,7-di-t-butyl-3- (3,4-di- Examples thereof include lactone antioxidants such as methyl-phenyl) -3H-benzofuran-2-one and vitamin E antioxidants such as the following formula (14).

(4) Other Additives In the propylene-based resin composition of the present invention, in addition to the above-mentioned components, ultraviolet absorbers, light stabilizers, neutralizers, and nuclei used as stabilizers for propylene-based polymers are included. An additive such as an agent can be blended.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 And ultraviolet absorbers such as' -hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.

  As the light stabilizer, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 ′ -Hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl succinate) ) Ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N'-bis (3-aminopropyl) ethylenediamine-2,4- Bis [N-butyl-N- ( , Mention may be made of a light stabilizer such as 2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, zinc stearate, and magnesium stearate, and hydrotalcite (trade name: DHT-4A, represented by the following formula (15) manufactured by Kyowa Chemical Industry Co., Ltd.). Magnesium aluminum composite hydroxide salt) and Mizukarak (trade name, lithium aluminum composite hydroxide salt represented by the following formula (16) manufactured by Mizusawa Chemical Industry Co., Ltd.).
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (15)
[Where x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]
[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (16)
[Wherein X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

  As the nucleating agent, a metal salt of an organic phosphoric acid ester, a metal salt of an organic monocarboxylic acid, a metal salt of an organic dicarboxylic acid, a polymer nucleating agent, dibenzylidene sorbitol or a derivative thereof, a metal salt of diterpenic acids, a triaminobenzene derivative and the like are used. .

  Examples of the organic phosphoric acid ester metal salts include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate and sodium-2,2'-ethylidene-bis (4,6 -Di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6 -Di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4 -Methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, nato Um-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium- 2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate Phosphate, calcium-bis [(2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-methylene-bis (4,6-di- t-butylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2′- Tylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2'- Ethylidene-bis (4-s-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'- Methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'- Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-ethylidene-bis (4,6-di-t-butyl) Phenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4,6 -Di-t-butylfel) phosphate], aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum hydroxy-bis [2,2'- Methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum dihydroxy-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate and the like. .

  Examples of the metal salt of an organic monocarboxylic acid include salts of a metal such as benzoic acid and allyl-substituted acetic acid, and specifically, benzoic acid, p-isopropylbenzoic acid, o-tert-butylbenzoic acid, Examples thereof include pt-butylbenzoic acid, monophenylacetic acid, diphenylacetic acid, phenyldimethylacetic acid, adipic acid, and Li, Na, Mg, Ca, Ba, and Al salts thereof. Examples of the organic dicarboxylic acid metal salts include, for example, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, phthalic acid, cyclohexanecarboxylic acid, norbornanedicarboxylic acid and their Li, Na, Mg, Ca, Ba, Al Salts and the like can be mentioned. Examples of the polymer nucleating agent include polyvinyl cyclohexane, poly-3-methyl-1-butene, and the like.

  Examples of the dibenzylidene sorbitol or a derivative thereof include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, and 1,3-benzylidene-2,4- p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4 -P-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4 -Di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn- (Ropybenzylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2 4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, , 3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1, 3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbe Dylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3,2,4- Examples thereof include di (p-chlorobenzylidene) sorbitol and 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol. Preferably, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol , 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] -nonitol and the like.

  The metal salt of diterpenic acids is a reaction product of diterpenic acids and a predetermined metal compound such as a magnesium compound and an aluminum compound. Diterpenic acid is a rosin generally known as a natural resin obtained from a Pinaceae plant, specifically, a natural rosin such as gum rosin, tall oil rosin, wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenation Various modified rosins such as rosin, polymerized rosin, α, β-ethylenically unsaturated carboxylic acid modified rosin, and purified products of the above-mentioned natural rosin and modified rosin can be obtained as raw materials. Examples of the diterpenic acids include pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid, and the like.

  Examples of the triaminobenzene derivatives include 1,3,5-tris [2,2-dimethylpropionylamino] benzene, 1,3,5-tris [cyclohexylcarbonylamino] benzene, and 1,3,5-tris [4- Methylbenzoylamino] benzene, 1,3,5-tris [3,4-dimethylbenzoylamino] benzene, 1,3,5-tris [3,5-dimethylbenzoylamino] benzene, 1,3,5-tris [ Cyclopentanecarbonylamino] benzene, 1,3,5-tris [1-adamantanecarbonylamino] benzene, 1,3,5-tris [2-methylpropionylamino] benzene, 1,3,5-tris [3,3 -Dimethylbutyrylamino] benzene, 1,3,5-tris [2-ethylbutyrylamino] benzene, 1,3,5 Tris [2,2-dimethylbutyrylamino] benzene, 1,3,5-tris [2-cyclohexyl-acetylamino] benzene, 1,3,5-tris [3-cyclohexyl-propionylamino] benzene, 1,3 , 5-Tris [4-cyclohexyl-butyrylamino] benzene, 1,3,5-tris [5-cyclohexyl-valeroylamino] benzene, 1-isobutyrylamino-3,5-bis [pivaloylamino] benzene, 2, 2-dimethylbutyrylamino-3,5-bis [pivaloylamino] benzene, 3,3-dimethylbutyrylamino-3,5-bis [pivaloylamino] benzene, 1,3-bis [isobutyrylamino] -5- Pivaloylaminobenzene, 1,3-bis [isobutyrylamino] -5- (2,2-dimethyl-butyi L) aminobenzene, 1,3-bis [isobutyrylamino] -5- (3,3-dimethyl-butyryl) aminobenzene, 1,3-bis [2,2-dimethylbutyrylamino] -5-pi Valoylaminobenzene, 1,3-bis [2,2-dimethylbutyrylamino] -5-isobutyrylaminobenzene, 1,3-bis [2,2-dimethylbutyrylamino] -5- (3 3-dimethylbutyryl) -aminobenzene, 1,3-bis [3,3-dimethylbutyrylamino] -5-pivaloylamino-benzene, 1,3-bis [3,3-dimethylbutyrylamino] -5- Isobutyryl-aminobenzene, 1,3-bis [3,3-dimethylbutyrylamino] -5- (2,2-dimethyl-butyrylamino) aminobenzene or 1,3,5-tris [3- (trimethyl Lucyl) propionylamino] benzene. Among them, 1,3,5-tris [2,2-dimethylpropionylamino] benzene is preferred.

  Among these, preferred nucleating agents are organic phosphoric acid ester metal salts, dibenzylidene sorbitol or derivatives thereof, and triaminobenzene derivatives. In addition, you may use these nucleating agents in combination of 2 or more types.

  Further, in addition to the above, various known additives such as a lubricant, a dispersant such as a fatty acid metal salt, a dye, a pigment and the like can be blended within a range not to impair the object of the present invention.

  Other polymers other than the propylene-based polymer (a), such as polyethylene, ethylene-propylene copolymer, and ethylene, as long as the properties such as the properties, functions, and transparency of the propylene-based resin composition of the present invention are not impaired. Homopolymers such as propylene-diene copolymers, ethylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, acrylate polymers, binary or ternary copolymers 1 to 30 parts by weight can be arbitrarily blended with the coalesc based on 100 parts by weight of the propylene-based polymer (a). Similarly, elastomers such as natural rubber, butyl rubber, diene rubber, EPM, EPDM, EBM, EHM, EOM, and PBM can be blended. Further, general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica can be used in combination.

[2] Production method of propylene-based resin composition The propylene-based resin composition of the present invention comprises a propylene-based polymer (a), a donor / acceptor-based antistatic agent (A) and, if necessary, other additives. Each predetermined amount is put into a tumbler, a V blender, a Henschel mixer (trade name), a super mixer, a ribbon blender or the like and mixed to obtain a powdery propylene-based resin composition. Further, the powdery propylene-based resin composition is melt-kneaded in a usual single-screw extruder, twin-screw extruder, Banbury mixer, Brabender, roll, kneader, or the like in a temperature range of 190 to 260 ° C., and granulated. Thereby, a pellet-like propylene-based resin composition can be obtained. Further, a propylene-based polymer (a), a donor / acceptor-based antistatic agent (A) and, if necessary, other additives are supplied to a plurality of hoppers or a main hopper upstream and at least one side feed supply port downstream. After feeding each of the plurality of hoppers or main hoppers and at least one side feed supply port of a single-screw extruder or a twin-screw extruder comprising, a predetermined amount is supplied to the single-screw extruder or the twin-screw extruder. Then, the mixture is melt-kneaded in a temperature range of 190 to 260 ° C. and granulated to obtain a pellet-like propylene-based resin composition.

[3] Method for Producing Propylene-Based Resin Molded Article The method for producing a propylene-based resin molded article of the present invention is a method for producing a propylene-based resin molded article through a production process in an atmosphere at a temperature of 60 to 160 ° C. It is characterized by obtaining. The shape of the propylene-based resin composition used may be a powder, a pellet, or a pellet (granulated product) obtained by melting or dissolving the pellet to form a desired shape.

Examples of the production process in an atmosphere at a temperature of 60 to 160 ° C. in the present invention include a drying process, a powder slush molding process, a powder sintering lamination molding process, and a heat treatment process such as annealing and heat setting. In these production processes, known production processes can be applied without any limitation. There is no particular limitation on the method of raising the temperature to reach a predetermined temperature range of 60 to 160 ° C. For example, when drying a pellet of a propylene-based resin composition containing a filler such as talc or performing powder slush molding using a powdery propylene-based resin composition, annealing or heat setting the propylene-based resin molded body When heat treatment is performed, heating is performed intentionally using a heat source. Also, when using particles of the propylene-based resin composition in the powder sintering additive manufacturing method of a 3D printer, the inside of the molding machine is unintentionally placed in a high-temperature and low-humidity atmosphere because the particles are sintered using laser or electric discharge. Below.
In the drying step, from the viewpoint of drying quality and work efficiency, the temperature is usually 60 to 160 ° C, more preferably 70 to 120 ° C, further preferably 80 to 120 ° C, particularly preferably 90 to 110 ° C. The drying treatment time is preferably 0.5 to 12 hours, more preferably 1 to 6 hours, and still more preferably 1 to 3 hours. In the heat treatment step such as annealing or heat setting, from the viewpoint of the quality of the molded body such as physical properties and dimensional accuracy and work efficiency, the temperature is usually 60 to 160 ° C, more preferably 70 to 120 ° C, and further preferably 80 to 120 ° C. C., particularly preferably in an atmosphere of 90 to 110 ° C., and the heat treatment time is preferably 10 to 180 minutes, more preferably 20 to 120 minutes, and still more preferably 30 to 60 minutes. In the production process under the atmosphere at the temperature of 60 to 160 ° C., particularly in the drying process, from the viewpoint of drying quality and work efficiency, it is preferable that the atmosphere is further under the atmosphere of the relative humidity of 0 to 30%. More preferably, the atmosphere is 20%.

  As a method for producing the propylene-based resin molded article of the present invention, that is, a method for molding the propylene-based resin composition, a conventionally known method can be used. For example, an injection molding method, an extrusion molding method, a blow molding method, a press molding method, a powder slush molding method, a powder sintering lamination molding method and the like can be mentioned. Regarding the extrusion molding method, a thermoformed body can be obtained by using an extruded body obtained by extrusion molding and further performing a thermoforming method such as a vacuum forming method, a pressure forming method, and a vacuum pressure forming method.

  Various molded articles can be produced by the method for producing a propylene-based resin molded article of the present invention. Examples of the obtained molded article include various shaped articles such as various containers and medical instruments, parts for vehicles, packaging films, sheets, fibers, tubes, foams, and the like, but are not limited thereto. It may be a layered body or a laminated body.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The physical property measuring methods used in the following Examples and Comparative Examples, and the propylene-based polymer (a), the donor / acceptor-based antistatic agent (A), and the known resin compounding agents are as follows.
<1. Measurement method>

(1) Preparation of Injection Molded Specimen for Evaluation of Physical Properties A test piece having a size of 120 mm × 120 mm × 1 mm in thickness for evaluation of physical properties was prepared by injection molding (resin temperature 220 ° C.) of a resin composition pellet using an injection molding machine. After the injection molding of the obtained test piece, the condition was adjusted for at least one day in a constant temperature room adjusted to a room temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% (JIS K7100: 1999), and injection molding for physical property evaluation was performed. A test piece was prepared.
(2) Ethylene content
The ethylene content in the random copolymer was measured by infrared spectroscopy using a propylene-ethylene random copolymer whose composition was examined by ¹³ C-NMR as a reference substance and a characteristic absorption band of 733 cm ⁻¹ (calibration curve). Create). Based on the calibration curve thus prepared, the ethylene content was measured by infrared spectroscopy using a sample of the propylene-based polymer (a) formed into a film having a thickness of about 500 μm by press molding.
Here, each content of propylene and ethylene as reference materials for preparing a calibration curve is a value measured by a ¹³ C-NMR method under the following conditions. The analysis of the ¹³ C-NMR spectrum was performed according to the analysis method described in JP-A-2006-307120, and the contents of propylene and ethylene were calculated.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300mg / 2mL
Solvent: orthodichlorobenzene

(3) Melt flow rate (MFR)
The measurement was performed at a test temperature of 230 ° C. and a nominal load of 2.16 kg in accordance with JIS K7210: 1999, Annex A, Table 1, Condition M.

(4) Surface resistivity A high-resistor IP high resistivity meter (MCP-HT260) manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used, the applied voltage was 10 V, and the electrodes were a double ring method (HRS probe). The value 60 seconds after the application of the voltage was adopted as the measured value. After the injection molding of the test piece, the test piece was subjected to condition control (JIS K7100: 1999) for at least one day in a constant temperature room controlled at a room temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5%. The surface resistivity was measured immediately after standing in a constant temperature bath at a temperature of 60 ° C., 80 ° C. or 90 ° C., and a relative humidity of 5% for 0.5 hour, 1 hour or 2 hours (annealing heat treatment step). The antistatic performance was evaluated.

<2. Resins, additives>
2-1. Physical properties of propylene-based polymer (a) (PP-1) Metallocene-based propylene-ethylene random copolymer Catalyst: Metallocene catalyst MFR: 30.0 g / 10 min Ethylene content: 0.9 wt%
(PP-2) Ziegler propylene-ethylene random copolymer catalyst: Ziegler catalyst MFR: 10.0 g / 10 min Ethylene content: 2.9 wt%

2-2. Antistatic agent 2-2-1
Donor / acceptor antistatic agent (A):
(T-1) a compound represented by the formula _{(2), mC 42 H 81} O 8 B + nC 23 H 48 ON 2 ( strain) boronic Laboratory trade name "Biomiseru BN-105"
(T-3) Compound represented by the above formula (3), mC ₄₂ H ₈₁ O ₈ B + nC ₂₃ H ₄₈ O ₂ N “Biomicel BN-77” (trade name, manufactured by Boron Research Laboratory Co., Ltd.)
2-2-2
Low molecular weight antistatic agent:
(T-2) Glyceryl monostearate “Electro stripper TS-5” manufactured by Kao Corporation

2-3. Other additives (A-1) Phenolic antioxidant "IR1010": tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxylphenyl) propionate] methane BASF Japan Ltd. Product name "IRGANOX1010"
(A-2) Phosphorus antioxidant "IF168": Tris (2,4-di-t-butylphenyl) phosphite BASF Japan Ltd. product name "IRGAFOS168"
(A-3) Neutralizing agent "CaSt": calcium stearate Nitto Kasei Corporation (A-4) Nucleating agent "NX8000J": 1,2,3-trideoxy-4,6: 5,7-bis- [(4-Propylphenyl) methylene] -Nonitol “Mirad NX8000J” manufactured by Milliken & Co.

3-1. Example 1, Comparative Example 1
The propylene-based polymer (a) and the additives were prepared in the mixing ratio (parts by weight) shown in Table 1, and after dry blending with a super mixer, using a TEM-35B twin screw extruder manufactured by Toshiba Machine Co., Ltd. The mixture was melt-kneaded at a die exit temperature of 220 ° C. and pelletized. Using the obtained pellets of the propylene-based resin composition, injection-molded test specimens for evaluating physical properties were prepared, and after conditioning for one day or more, surface resistivity before and after standing at 80 ° C. and 5% RH for 1 hour. The value was measured. Table 1 shows the evaluation results.

3-2. Examples 2 to 6, Comparative Example 2
The surface resistivity was measured in the same manner as in Example 1 except that the heat treatment conditions of high temperature and low humidity were changed to the conditions shown in Table 2. Table 2 shows the evaluation results.

  From Table 1, it can be seen from the comparison between Example 1 and Comparative Example 1 that the surface specific resistance value after standing at 80 ° C. for 1 hour greatly changed from the initial value due to the inclusion of the donor-acceptor antistatic agent (A). It turns out not to be. On the other hand, for Comparative Example 1 using glyceryl monostearate which is a low molecular weight type antistatic agent which is not a donor / acceptor type antistatic agent, the initial value is that containing the donor / acceptor type antistatic agent (A). Despite being equivalent to the above, it can be seen that the surface resistivity after standing at 80 ° C. for 1 hour exceeds the measurable upper limit, that is, the antistatic performance has disappeared.

Further, from Table 2, even when the type and content of only the antistatic agent were changed in the propylene-based resin composition having the same composition as the additives other than the antistatic agent, various donors of Examples 2 to 6 were used. It can be seen that the surface resistivity of the acceptor antistatic agent (A) does not significantly change even after being left at 60 ° C. for 1 hour or 2 hours, that is, it retains the antistatic effect.
Further, in the case where biomicel BN-105 was used as the donor / acceptor antistatic agent (A) in Examples 2 to 4, the surface specificity was maintained even after standing at 80 ° C. or 90 ° C. for 0.5 hour or 1 hour. The resistance does not change much. When biomicel BN-77 was used as the donor-acceptor antistatic agent (A) in Examples 5 to 6, the content was low in Example 5 at 80 ° C, and in Examples 5 to 6 at 90 ° C. , The surface resistivity exceeds the measurable upper limit. From this, it can be seen that it is more preferable to use BN-105 under conditions exceeding 80 ° C.
On the other hand, in Comparative Example 2 using glyceryl monostearate, it can be seen that the surface specific resistance value exceeds the measurable upper limit value under any temperature condition, that is, the antistatic performance is lost.
As is apparent from the above, by adding a specific donor / acceptor antistatic agent to the propylene-based polymer at a predetermined ratio, the physical properties of the propylene-based resin composition are not impaired, and a complicated process is added. Instead, a molded article can be obtained while maintaining good antistatic performance in a high-temperature and low-humidity environment.

  The present invention uses a propylene-based resin composition containing a specific donor / acceptor-based antistatic agent in a predetermined ratio, without impairing the physical properties of the propylene-based resin composition, and adds a complicated process. Instead, a method for producing a propylene-based resin molded article capable of obtaining a molded article while maintaining good antistatic performance under a high-temperature and low-humidity environment has been found to be useful.

Claims (4)

A half having at least one atomic group represented by the following formula (1) and at least one straight-chain hydrocarbon group having 5 to 28 carbon atoms in the molecule per 100 parts by weight of the propylene-based polymer (a). Donor comprising at least one kind of a polar organic compound and at least one kind of a basic organic compound having one basic nitrogen atom group and at least one straight-chain hydrocarbon group having 5 to 28 carbon atoms in a molecule. Using a propylene-based resin composition containing 0.01 to 3 parts by weight of the acceptor-based antistatic agent (A) to obtain a molded article through a production process in an atmosphere at a temperature of 60 to 160 ° C. A method for producing a propylene-based resin molded product.
The method for producing a propylene-based resin molded article according to claim 1, wherein the donor-acceptor antistatic agent (A) is a compound represented by the following formula (2) or a compound represented by the following formula (3).
(Wherein, R ¹ and R ² are each independently R ⁷ CO—OCH ₂ — or HOCH ₂ —, and at least one is R ⁷ CO—OCH ₂ —; and R ³ and R ⁴ are Each independently is CH ₃ —, C ₂ H ₅ —, HOCH ₂ —, HOC ₂ H ₄ — or HOCH ₂ CH (CH ₃ ) —, and R ⁵ is —C ₂ H ₄ — or —C ₃ H _6- , and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbons.)
(Wherein, R ¹ and R ² are each independently R ⁷ CO—OCH ₂ — or HOCH ₂ —, and at least one is R ⁷ CO—OCH ₂ —; and R ³ and R ⁴ are Each independently is CH ₃ —, C ₂ H ₅ —, HOCH ₂ —, HOC ₂ H ₄ — or HOCH ₂ CH (CH ₃ ) —, and R ⁵ is —C ₂ H ₄ — or —C ₃ H _6- , and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbons.)   The method for producing a propylene-based resin molded product according to claim 1 or 2, wherein the molded product is obtained through a production process in an atmosphere having a relative humidity of 0 to 30%.   The method for producing a propylene-based resin molded product according to any one of claims 1 to 3, wherein the molded product is obtained through a production process in an atmosphere at a temperature of 70 to 120C.