JPH0967481A - Syndiotactic polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent moldability and transparency by compounding a syndiotactic polypropylene with a diamine/ monocarboxylic acid condensation product and/or a diamine/monocarboxylic acid/polybasic acid polycondensation product. SOLUTION: This resin composition is produced by compounding (A) 100 pts.wt. of a syndiotactic polypropylene with (B) 0.001-10 pts.wt. of a diamine/ monocarboxylic acid condensation product and/or a diamine/monocarboxylic acid/polybasic acid polycondensation product. The component A is preferably a propylene homopolymer and/or a copolymer of propylene and ethylene and/or a >=4C α-olefin. Preferably, the diamine in the component B is ethylenediamine, the monocarboxylic acid is stearic acid or behenic acid and the polybasic acid is a >=2-basic carboxylic acid such as sebacic acid. The moldability and transparency can further be improved by the addition of an organic crystal-nucleation agent such as an organic phosphoric acid salt and/or an inorganic crystal- nucleation agent such as talc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a syndiotactic polypropylene resin composition, and more specifically, it has excellent moldability such as fluidity and releasability, and excellent optical properties such as transparency and gloss. And a syndiotactic polypropylene resin composition having good mechanical properties such as rigidity and impact resistance.

[0002]

2. Description of the Related Art Syndiotactic polypropylene has excellent properties such as transparency, impact resistance, and electrical characteristics, but has a drawback that the curing speed is slow and molding (especially injection molding) is difficult.

In order to accelerate the curing rate of crystalline polypropylene, there is a method of adding a crystal nucleating agent. However, typical organic nucleating agents such as conventionally known metal salts of aromatic carboxylic acids (such as GBA), sorbitol derivatives (such as gelol MD) and organic phosphates (such as NA-21),
In addition, when an inorganic nucleating agent such as talc is added to crystalline polypropylene, the crystallization rate increases, and the transparency of isotactic polypropylene is often improved, but the transparency is still insufficient. In the case of syndiotactic polypropylene, there was a problem that the crystallization rate was not sufficient and the transparency was rather lowered by the addition of the nucleating agent added to the isotactic polypropylene.

It is known to improve the slip and blocking resistance of films by adding a diamine / monocarboxylic acid condensate to isotactic polypropylene.

Further, JP-A-6-220268 discloses a composition obtained by adding a diamine / monocarboxylic acid / polybasic acid polycondensate to isotactic polypropylene. It is described that addition of the above diamine / monocarboxylic acid / polybasic acid polycondensate to isotactic polypropylene improves the fluidity of the resin and the heat resistance and impact resistance of the molded product. .

However, since isotactic polypropylene has a high crystallization rate and good moldability, there is almost no problem of poor releasability caused by a low crystallization rate. Even with the above-mentioned known techniques, the fluidity of the resin and the film The purpose is to improve the slip property and the heat resistance and impact resistance of the molded product.

[0007]

On the other hand, although syndiotactic polypropylene has various excellent physical properties such as transparency, impact resistance, and electrical characteristics, it is processed due to its slow crystallization rate. There is a peculiar problem of syndiotactic polypropylene, which is poor property, and it is a major problem that must be solved before it can be put to practical use in the field of injection molding. This problem is a problem not found in isotactic polypropylene.

An object of the present invention is to provide a composition in which the moldability of syndiotactic polypropylene is improved and the resulting molded article has good transparency.

[0009]

[Means for Solving the Problems] The present inventors completed the present invention by earnestly searching to solve the above problems. That is, the present invention relates to syndiotactic polypropylene 10
0 parts by weight with diamine / monocarboxylic acid condensate or diamine / monocarboxylic acid / polybasic acid polycondensate 0.001
It is to provide a syndiotactic polypropylene resin composition comprising 10 to 10 parts by weight and having excellent moldability.

The present invention also provides a composition in which the syndiotactic polypropylene is a syndiotactic polypropylene homopolymer or a copolymer of propylene having a syndiotactic structure and ethylene and / or another olefin. Especially.

The present invention also provides a syndiotactic polypropylene composition in which the diamine / monocarboxylic acid condensate is an ethylenediamine / stearic acid condensate.

Another object of the present invention is to provide the above syndiotactic polypropylene resin composition, wherein the dicondensate, monocarboxylic acid and polybasic acid polycondensate are ethylenediamine, stearic acid and sebacic acid polycondensate.

The present invention further relates to an organic crystallization nucleating agent and / or
Another object of the present invention is to provide the syndiotactic polypropylene resin composition as described above, which further comprises 0.001 to 1 part by weight of an inorganic crystallization nucleating agent with respect to 100 parts by weight of syndiotactic polypropylene.

Further, the present invention further comprises 1 part of isotactic propylene (co) polymer in 100 parts by weight of the above composition.
It is intended to provide a syndiotactic polypropylene resin composition containing 100 parts by weight or less.

[0015]

The syndiotactic polypropylene used in the present invention is not only a propylene homopolymer but also a copolymer of propylene and ethylene and / or an α-olefin having 4 or more carbon atoms or a mixture thereof. is there.

Of these syndiotactic polypropylenes, the preferred syndiotactic polypropylene is rr at about 20.2 ppm based on tetramethylsilane in the spectrum measured by ¹³ C-NMR.
The syndiotactic pentad fraction obtained as the ratio of the peak intensity attributed to the absorption of rr to the total absorption intensity of all methyl carbons of polypropylene is 0.6 or more, preferably 0.7 for the propylene homopolymer.
The above is ¹³ C-N in the copolymer of propylene and ethylene and / or other α-olefin other than propylene.
In the spectrum measured by MR, the intensity of the rrrr peak attributed to the syndiotactic structure, which appears at about 20.2 ppm with respect to tetramethylsilane as a reference, is calculated as the ratio to the total absorption intensity of all methyl carbons in the copolymer. A value of 0.3 or more, preferably 0.5 or more is used.

Further, the content of the α-olefin other than ethylene and / or propylene in the above-mentioned copolymer having a syndiotactic structure of propylene and other α-olefin is preferably 0 based on the whole polymer. .1
It is 20% by weight, more preferably 0.1 to 10% by weight. When the amount of ethylene and / or α-olefin exceeds 20% by weight, the rigidity of the obtained molded product of the copolymer decreases.

As the above α-olefin, a linear or branched α-olefin having 4 to 20 carbon atoms is used, and specifically, butene-1, pentene-1, hexene-1, and heptene- are used.
Linear olefins such as 1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, pentadecene-1, octadecene-1, and 3-
Methylbutene-1,4-methylpentene-1,4,4-
A branched olefin such as dimethylpentene-1 is exemplified.

The above syndiotactic polypropylene can be produced by a known method. A. Ew
en reference (J. Am. Chem. Soc., vol.
110,6255- 6256 (1988)) and isopropyl (cyclopentadienyl-fluorenyl) zirconium dichloride and methylaluminoxane (MA).
O) a catalyst, and EP387690 publication, EP
It is produced by (co) polymerization using a catalyst composed of a metallocene compound and methylaluminoxane described in Japanese Patent No. 387691.

In the method of the present invention, isotactic polypropylene may be added in addition to syndiotactic polypropylene. The isotactic polypropylene mixed at that time may be a homopolymer of propylene or a copolymer of propylene and ethylene and / or α-olefin, and the mixing ratio is 0 with respect to 100 parts by weight of syndiotactic polypropylene. 1 to 100 parts by weight, preferably 1 to 50 parts by weight, and more preferably 5 to 30 parts by weight.

The addition of isotactic polypropylene further improves the rigidity and processability of the resin composition. This isotactic polypropylene is industrially available.

In addition to isotactic polypropylene, copolymers of ethylene and α-olefins (including propylene) and α-olefin homopolymers other than propylene can be added to the composition of the present invention. Particularly preferred is an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms at a ratio of 40:60 to 95: 5 (weight ratio) of ethylene: α-olefin using a homogeneous catalyst. ,
Alternatively, it is an α-olefin polymer having 4 or more carbon atoms. The amount added is 0 to 50% by weight, preferably 0 to 30% by weight.
% By weight. In particular, the impact resistance is improved by adding the above copolymer.

In the present invention, the diamine / monocarboxylic acid condensate is generally easily available on the market. The polycondensate of diamine / monocarboxylic acid / polybasic acid is produced by a method for producing a high softening point wax as described in, for example, JP-A-3-153793.

The diamine which can be used here has 1 to 1 carbon atoms.
It is a diamine having 10 carbon atoms, and examples thereof include ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, paraxylenediamine, and isophoronediamine. Among them, ethylenediamine is particularly preferable.

The monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid having 10 or more carbon atoms and a hydroxymonocarboxylic acid. Examples thereof include stearic acid, behenic acid, montanic acid and palmitic acid. Among them, stearic acid and Behenic acid is particularly preferred.

The amount of the diamine used when producing the diamine / monocarboxylic acid condensate is about 1 mol per 1 mol of the monocarboxylic acid, and the diamine is used so that the amino groups are equivalent to the carboxyl groups. . When a polybasic acid is used in the production of a diamine / monocarboxylic acid / polybasic acid polycondensate, the amount used is such that the amino groups are equivalent to the total carboxyl groups of the monocarboxylic acid and polybasic acid. Can be decided

When a polybasic acid is contained, a dibasic acid or more carboxylic acid is preferably used as the polybasic acid. Specifically, it is an aliphatic dicarboxylic acid such as sebacic acid or adipic acid, or an aromatic terephthalic acid or the like. Examples thereof include dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexylsuccinic acid.

The melting point of the polycondensate of diamine / monocarboxylic acid / polybasic acid can be adjusted depending on the type of monocarboxylic acid used, but the amount of polybasic acid used is fixed for a given monocarboxylic acid. It can also be adjusted by changing it. In particular, when a polybasic acid is used, the melting point of the polycondensate is increased and the effect of the present invention can be further exhibited.

When a (poly) condensate having a high melting point is used, the mold releasability is good, but the dispersibility with the resin tends to be poor. The melting point of the carboxylic acid condensate or the diamine / monocarboxylic acid / polybasic acid polycondensate is preferably 1
30-280 degreeC, More preferably, it is 130-220 degreeC.

In the present invention, particularly when a polycondensate of diamine / monocarboxylic acid / polybasic acid is used, the melting point is higher than that of the condensate of diamine / monocarboxylic acid. However, it does not easily float on the resin surface and can be preferably used for medical and food applications that require heat sterilization.

The amount of polybasic acid used is usually 0.18 mol to 1.0 mol per 2 mol of monocarboxylic acid. When the amount of polybasic acid is more than 1 mol, a carboxyl group remains at the end of the product, which causes decomposition of polypropylene, which is not preferable. The (poly) condensate used in the present invention is, for example, as a method for producing an ethylenediamine / stearic acid / sebacic acid polycondensate, 2 mol of stearic acid and 1 mol of sebacic acid are heated and melted, 2 mol of ethylenediamine is added dropwise, and nitrogen is added. It is obtained by starting the dehydration reaction at 160 ° C. in an atmosphere, reacting at 250 to 260 ° C. for 7 hours until the amine value becomes 5 or less, and taking out and hardening.

In the reaction, phosphorous acid or hypophosphorous acid may be added as a color preventing agent. The amine value of the reaction product is 10 or less, preferably 5 or less.

The syndiotactic polypropylene resin composition of the present invention comprises a diamine / monocarboxylic acid condensate and / or diamine / monocarboxylic acid / polybasic acid polycondensate 0.001 based on 100 parts by weight of the above syndiotactic polypropylene. 10 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 2 parts by weight. In particular, when the composition of the present invention is used in a film, a fish eye may be produced even when 0.2 parts by weight or more, and further 3 parts by weight or more are added as in the case of using a general crystallization nucleating agent. In addition, the slipperiness of the film is improved, and the heat shrinkability can be reduced.

If the amount of the diamine / monocarboxylic acid polycondensate and / or the diamine / monocarboxylic acid / polybasic acid polycondensate to be added is less than 0.001 part by weight, the effect of addition is not exhibited. If it is used in excess of 10 parts by weight, the dispersibility will be poor and the rigidity and transparency will be poor.

In the present invention, if necessary, an organic crystallization nucleating agent and / or an inorganic crystallization nucleating agent is added in an amount of 0.001 to 100 parts by weight with respect to 100 parts by weight of syndiotactic polypropylene.
1 part by weight, preferably 0.01 to 0.5 part by weight is added.

By mixing together the additive used in the present invention and the above-mentioned organic crystallization nucleating agent and / or inorganic crystallization nucleating agent, moldability (release property) and transparency are further improved.

In the present invention, as a conventional nucleating agent which is optionally used in combination, a sorbitol derivative (for example, Shin Nippon Rika Co., Ltd., trade name Gelol MD) and an organic phosphate (for example, Asahi Denka Co., Ltd.) are used. Product name NA- manufactured by Kogyo Co., Ltd.
21) and the like, organic crystallization nucleating agents such as talc and kaolin, and polymer nucleating agents such as polyvinyl cyclohexane.

The method for preparing the composition of the present invention is not particularly limited, and the method generally used for mixing polyolefin and additives can be used as it is. For example, it is common to use a Henschel or the like to mix at a temperature not higher than the melting point of polypropylene and then melt-mix with an extruder or the like. Upon mixing these, stabilizers such as an antioxidant and an ultraviolet absorber which are usually used for crystalline polypropylene may be mixed at the same time.

The resin composition of the present invention can further improve transparency, which is a major feature of syndiotactic polypropylene, or can improve moldability without impairing it. Particularly, in injection molding, not only the curing speed of the resin in the mold is increased, but also the mold releasability from the mold is improved, so that the molding cycle can be significantly shortened.

[0040]

EXAMPLES The present invention is described in detail below with reference to examples, but the present invention is not limited to the following examples.

The physical properties of the syndiotactic polypropylene resin compositions obtained in Examples and Comparative Examples were evaluated as follows. (1) Crystallization temperature (Tc): Using a differential scanning calorimeter, the polypropylene resin composition was heated and melted at 240 ° C. for 10 minutes and then cooled at a rate of 30 ° C./min, and observed as heat generated by crystallization. The temperature of the peak was measured. (2) Melt flow index (MFI: g / 10
Min): Measured at 230 ° C. under a load of 2.16 kg according to ASTM-D1238. (3) Releasability (t _min : seconds): A cylindrical molded product (outer diameter φ = 32 mm, meat) with one side closed under conditions of a resin temperature of 280 ° C. and a mold temperature of 39 ° C. using an injection molding machine. The cooling time t _min required to remove from the mold when injection molding (2 mm thickness) was expressed. (4) Haze (%): Measured according to JIS-K6714 for a sheet having a 50 mm square and a thickness of 2 mm. (5) Tensile yield strength (kg / cm ² ): ASTM-D
638 (23 ° C). (6) Elongation (%): Based on ASTM-D638 (23 ° C). (7) Izod (with notch) impact strength (kg ・ cm
/ Cm): Based on JIS-K7100.

The respective blends were mixed with a mixer for 5 minutes, and then pelletized using an extruder under the conditions of a resin temperature of 230 ° C. and a rotation speed of 80 rpm. Using an injection molding machine, a test piece having a thickness of 2 mm was prepared at a cylinder temperature of 250 ° C. and a mold temperature of 40 ° C., and various tests were performed using the test piece.

Example 1 A bulk polymerization method of propylene in the presence of hydrogen using a catalyst consisting of diphenylmethylene (cyclopentadienyl) fluorenyl zirconium dichloride and methylaluminoxane according to the method described in JP-A-2-274763. Syndiotactic polypropylene (MFI at 230 ° C. 1.76 g / 10 min, syndiotactic pentad fraction 0.822, crystallization temperature T
c is 53 ° C., hereinafter referred to as s-PP) 100 parts by weight, and 0.10 parts by weight of Irgaphos 168 (manufactured by Ciba Geigy) and Irganox 1010 as antioxidants.
(Ciba Geigy) 0.045 parts by weight, calcium stearate 0.10 parts by weight as a neutralizing agent, ethylenediamine / stearic acid / sebacic acid polycondensate (manufactured by Kyoeisha Chemical Co., Ltd .: trade name: Light Amide Series) WH2
15 (hereinafter referred to as WH215): 0.30 part by weight of a melting point of 215 ° C., a molecular weight of about 700) was added, mixed with a Henschel mixer, and then granulated with an extruder to obtain a syndiotactic polypropylene resin composition. It was The composition had a crystallization temperature Tc of 68 ° C., a mold release time of 22 seconds, an MFI of 1.93 g / 10 minutes and a haze of 17%, and has good moldability and excellent transparency. The results are shown in Table 1.

Example 2 A syndiotactic polypropylene resin composition was obtained in the same manner as in Example 1 except that WH215 was changed to 0.05 parts by weight with respect to 100 parts by weight of s-PP. The crystallization temperature Tc of this composition was 63 ° C. The results are shown in Table 1.

Example 3 A syndiotactic polypropylene resin composition was obtained in the same manner as in Example 1 except that WH215 was changed to 3.00 parts by weight with respect to 100 parts by weight of s-PP. The crystallization temperature Tc of this composition was 69 ° C. The results are shown in Table 1.

Comparative Example 1 A syndiotactic polypropylene resin composition obtained by adding only an antioxidant or a neutralizing agent to s-PP without using WH215 was evaluated in the same manner as in Example 1. The crystallization temperature Tc of this composition was 53 ° C., the mold release time was 65 seconds or more, and the MFI was 1.76 g / 10 minutes, which was difficult to mold and was not suitable for use for injection molding. The results are shown in Table 1.

Example 4 0.20 parts by weight of WH215 was added to 100 parts by weight of s-PP, and a sorbitol derivative (Shin-Nippon Rika Co., Ltd.).
A syndiotactic polypropylene resin composition part was obtained in the same manner as in Example 1 except that 0.20 part by weight of the product (manufactured by: Gelall MD) was added. The crystallization temperature Tc of this composition was 72 ° C. The results are shown in Table 1.

Comparative Example 2 The same as Example 4 except that 0.20 part by weight of sorbitol derivative (Shin Nippon Rika Co., Ltd., Gelol MD) was used without using WH215, relative to 100 parts by weight of s-PP. Then, the syndiotactic polypropylene resin composition was obtained and evaluated. The crystallization temperature Tc of this composition is 72.
Although the temperature rose to ℃, the releasability was poor. The results are shown in Table 1.

Example 5 With respect to 100 parts by weight of s-PP, an ethylenediamine / stearic acid / sebacic acid polycondensate (Light Amide series WH255, manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Amide series WH25 was used instead of WH215.
5 (hereinafter referred to as WH255) having a melting point of 255 ° C. and a molecular weight of about 850) was added in the same manner as in Example 1 except that 0.20 part by weight was added to obtain a syndiotactic polypropylene resin composition. The crystallization temperature Tc of this composition is 69 ° C., and it has good moldability and excellent transparency. The results are shown in Table 1.
Shown in

Example 6 0.10 parts by weight of WH255 was added to 100 parts by weight of s-PP, and an organic phosphate (N, manufactured by Asahi Denka Kogyo Co., Ltd., N
A-21) A syndiotactic polypropylene resin composition was obtained in the same manner as in Example 5, except that 0.10 part by weight was added. The crystallization temperature Tc of this composition was 72 ° C. The results are shown in Table 1.

Example 7 Isotactic polypropylene obtained by polymerizing 90 parts by weight of s-PP with a Solvay catalyst (manufactured by Mitsui Toatsu Chemicals, Inc., trade name: noblen J3H-S3000, 23)
MFI at 0 ° C. was 13.0 g / 10 minutes, and 10 parts by weight of iPP) was mixed with WH215 of 0.3.
A syndiotactic polypropylene resin composition was obtained in the same manner as in Example 1 except that 0 part by weight was added. The crystallization temperature Tc of this composition was 81 ° C. The results are shown in Table 1.

Comparative Example 3 90 parts by weight of s-PP was mixed with 10 parts by weight of iPP, and WH was mixed.
The same procedure as in Example 7 was performed without using 215 to obtain a syndiotactic polypropylene resin composition. The crystallization temperature Tc of this composition rose to 81 ° C. and the demolding time was 4
It was shortened to 3 seconds and the moldability was improved to some extent, but the transparency was deteriorated. The results are shown in Table 1.

Example 8 A syndiotactic polypropylene resin composition was obtained in the same manner as in Example 7 except that 20 parts by weight of iPP was mixed with 80 parts by weight of s-PP. The crystallization temperature Tc of this composition was 87 ° C. The results are shown in Table 1.

Example 9 Ethylenediamine / stearic acid condensate (ethylene bis-stearic acid amide E based on 100 parts by weight of s-PP)
A syndiotactic polypropylene resin composition was obtained in the same manner as in Example 1 except that 0.20 part by weight of BS, melting point 140 ° C., molecular weight 592, manufactured by Lion Corporation, hereinafter referred to as EBS) was added. . Crystallization temperature T of this composition
c was 69 ° C. The results are shown in Table 1.

[0055]

[Table 1]

[0056]

INDUSTRIAL APPLICABILITY The syndiotactic polypropylene resin composition of the present invention has good mold releasability from a mold, excellent transparency, and good physical property balance, particularly in injection molding.

Claims (4)

[Claims] 1. A syndiotactic polypropylene 10
0 parts by weight, diamine / monocarboxylic acid condensate, and /
Or diamine / monocarboxylic acid / polybasic acid polycondensate 0.
A syndiotactic polypropylene resin composition comprising 001 to 10 parts by weight and having excellent moldability. 2. The syndiotactic polypropylene,
The syndiotactic polypropylene resin composition according to claim 1, which is a syndiotactic polypropylene homopolymer and / or a copolymer of propylene having a syndiotactic structure and ethylene and / or another olefin. 3. The organic crystallization nucleating agent and / or the inorganic crystallization nucleating agent is further added in an amount of 0.001 to 1 part by weight based on 100 parts by weight of syndiotactic polypropylene. Syndiotactic polypropylene resin composition. 4. 100 parts by weight of the composition according to claim 1 further comprising 100 parts of an isotactic propylene (co) polymer.
A syndiotactic polypropylene resin composition added in an amount of not more than parts by weight.