JP3364004B2 - Crystal nucleating agent for polyolefin and polyolefin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin crystal nucleating agent, and more particularly to a polyolefin crystal nucleating agent that accelerates the crystallization rate of polyolefin.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polyolefins represented by polyethylene and polypropylene have excellent processability, chemical resistance, electrical properties and mechanical properties.
It is processed into injection molded products, hollow molded products, films, sheets, fibers, etc. and used for various purposes. However, depending on the application, the rigidity, heat resistance and transparency may not be sufficient.

It is known that the rigidity, heat resistance rigidity and transparency of the molded product made of such a polyolefin can be improved if the crystallization speed of the polyolefin can be increased and fine crystals can be rapidly generated during the molding process. ing.
Therefore, in order to accelerate the crystallization rate of the polyolefin, it has been performed to add a crystal nucleating agent to the polyolefin, for example, sodium adipate, para-t-
Aluminum salts of butylbenzoic acid, dibenzylidene sorbitol, and metal salts of alkylphenol phosphates are used.

However, the conventional crystal nucleating agent does not always have a sufficient effect of improving the crystallization rate, and the resulting molded article has mechanical properties such as rigidity and heat resistance, or optical properties such as transparency and gloss. I was not always satisfied.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and improves the crystallization rate of polyolefin to obtain a molded article excellent in mechanical properties and / or optical properties. It is an object of the present invention to provide a crystal nucleating agent for polyolefin that can be obtained.

[0006]

SUMMARY OF THE INVENTION The first crystal nucleating agent for polyolefin according to the present invention is characterized by containing a metal salt of rosin as a main component.

In the present invention, the rosin is preferably at least one rosin selected from the group consisting of natural rosin, modified rosin and purified products thereof. The metal salt is preferably at least one metal salt selected from the group consisting of sodium salt, potassium salt and magnesium salt. Further, the metal salt of rosin is preferably at least one metal salt of rosin selected from the group consisting of metal salt of dehydroabietic acid, metal salt of dihydroabietic acid and metal salt of dihydropimaric acid.

The second polyolefin crystal nucleating agent according to the present invention is characterized by comprising a compound represented by the following formula (I) and / or a metal salt thereof.

[0009]

[Chemical 2]

(In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, which may be the same or different) In the compound represented by (I) and / or its metal salt, R ¹ is an isopropyl group,
Compounds in which R ² and R ³ are methyl groups and / or metal salts thereof are preferred. The metal salt of the compound represented by the formula (I) is preferably at least one metal salt selected from the group consisting of sodium salt, potassium salt and magnesium salt. Further, the metal salt of the compound represented by the formula (I) is selected from the group consisting of a sodium salt, a potassium salt or a magnesium salt of a compound in which R ¹ is an isopropyl group and R ² and R ³ are methyl groups. More preferably, it is at least one metal salt.

Since the crystal nucleating agent for polyolefin of the present invention improves the crystallization rate of polyolefin and makes the crystals finer, it is possible to obtain a molded product having excellent mechanical properties and / or optical properties. The polyolefin containing the crystal nucleating agent for polyolefin of the present invention is widely used from household products to industrial products, for example, it is preferably used as a material for food containers, electric parts, electronic parts, automobile parts, machine mechanism parts, etc. It

[0012]

DETAILED DESCRIPTION OF THE INVENTION The crystal nucleating agent for polyolefin according to the present invention will be specifically described below. The first crystal nucleating agent for polyolefin according to the present invention is a crystal nucleating agent containing a metal salt of rosin as a main component, and the metal salt of rosin is 5 to 100% by weight, preferably 10 to 100% by weight. It is contained in the ratio of.

In the present invention, the metal salt of rosin means a reaction product of a rosin and a metal compound. As rosins, natural rosins such as gum rosin, tall oil rosin and wood rosin; various modifications such as disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin and α, β-ethylenically unsaturated carboxylic acid modified rosin Rosin; examples include a purified product of the natural rosin and a purified product of modified rosin. The unsaturated carboxylic acid used in the preparation of the α, β-ethylenically unsaturated carboxylic acid-modified rosin includes, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid. , Methacrylic acid and the like. Among these,
At least one rosin selected from the group consisting of natural rosin, modified rosin, purified product of natural rosin, and purified product of modified rosin is preferable. Here, rosins are pimaric acid, sandaracopimaric acid, parastophosphoric acid,
Isopimaric acid, abietic acid, dehydroabietic acid,
It contains a plurality of resin acids selected from neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid and the like.

Examples of the metal compound which reacts with the rosin to form a metal salt include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin. Specific examples thereof include chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides of the above metals.

In the present invention, the metal salt of rosin is at least one metal salt of rosin selected from the group consisting of sodium salt of rosin, potassium salt of rosin and magnesium salt of rosin. It is preferable. Further, the metal salt of rosin is preferably at least one metal salt of rosin selected from the group consisting of metal salts of hydrogenated rosin, metal salts of disproportionated rosin and metal salts of dehydrogenated rosin. Among these, at least one metal salt of rosins selected from the group consisting of metal salts of dehydroabietic acid, metal salts of dihydroabietic acid and metal salts of dihydropimaric acid is preferable.

As a method for producing such a metal salt of rosin, a conventionally known method can be adopted. For example, (1) the rosin and the metal compound are directly reacted in the presence or absence of an organic solvent. Method (Direct Method) (2) A method of reacting a metal salt of a rosin with the metal compound in the presence of water and / or an organic solvent to carry out salt exchange (metathesis method) and the like can be mentioned.

When the direct method is adopted, it is preferable that the rosins are dissolved in an organic solvent and reacted with the metal compound in a solution state in consideration of yield and workability. Examples of the organic solvent used here include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. This organic solvent is used in consideration of solubility with respect to rosins, water separability and the like.

The amount of the organic solvent used for reacting the rosin with the metal compound is not particularly limited, but is usually about 20 to 500 parts by weight per 100 parts by weight of the rosin used. The reaction temperature is not particularly limited,
It is usually in the range of about 40 to 150 ° C, preferably 50 to 120 ° C. The reaction between the rosin and the metal compound is usually carried out with the amount of metal introduced to the carboxyl group of the rosin being 5 to 10
It is carried out so as to be 0 equivalent%, preferably 10 to 100 equivalent%. After completion of the reaction, the organic solvent is distilled off to obtain the desired metal salt of rosin. The obtained metal salt of rosin may be purified if necessary.

When the metathesis method is adopted, considering the yield and workability, the metal salt of the rosin (for example, an alkali metal salt) is dissolved in an organic solvent, and a different metal is present in the presence of water. It is preferred to react with the compound. The organic solvent used here may be the same as the organic solvent used in the direct method. This organic solvent is used in consideration of the solubility of rosins in metal salts, water separability and the like.

The amount of the organic solvent used in reacting the metal salt of the rosin with the metal compound is not particularly limited,
Usually, it is 10 per 100 parts by weight of the metal salt of rosins.
It is about 0 to 1000 parts by weight. The reaction temperature is not particularly limited, but is usually about 40 to 150 ° C, preferably 50 to 90 ° C. After completion of the reaction, the organic solvent and water are distilled off to obtain the desired metal salt of rosin. The obtained metal salt of rosin may be purified if necessary.

The metal salt of the rosin thus obtained is preferably made into fine particles and used as a crystal nucleating agent. By making the metal salt of the rosin fine particles, the dispersibility in the polyolefin is improved, so that the metal salt of the rosin can be uniformly dispersed. As a method for micronizing the metal salt of rosins, a conventionally known method can be adopted, for example, (a) a method of pulverizing a solid of the obtained metal salt of rosins by a wet or dry method (b). After the reaction between the rosin and the metal compound is completed,
Without distilling off the organic solvent, water and, if necessary, a surfactant and / or a water-soluble polymer are added in a solution state, followed by emulsification and dispersion, and then the water and the organic solvent are distilled off. The method of doing is mentioned.

As the surfactant and / or the water-soluble polymer used in the method (b), those known in the art can be used. More specifically, a nonionic surfactant,
Examples thereof include anionic surfactants, polyvinyl alcohol, poly (meth) acrylic acid alkali metal salts, (meth) acrylic acid-acrylamide copolymers, water-soluble cellulose, starch and the like. In the method (b), the surfactant and the water-soluble polymer may be removed from the metal salt of rosins by distilling water and the organic solvent and then washing with water.

The second crystal nucleating agent for polyolefin according to the present invention is a compound represented by the following formula (I) and / or a metal salt of the compound represented by the following formula (I).

[0024]

[Chemical 3]

In the formula, R ¹ , R ² and R ³ are a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. Specific examples of the alkyl group include methyl, ethyl, n-
C1-C1 such as propyl, i-propyl, n-butyl, i-butyl, tert-butyl, pentyl, heptyl, octyl
8 alkyl groups, and these groups may have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group and a halogen.

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl. These groups are substituents such as hydroxyl group, carboxyl group, alkoxy group and halogen. May have.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group and naphthyl group, and these groups have substituents such as hydroxyl group, carboxyl group, alkoxy group and halogen. You may have.

The groups represented by R ¹ , R ² and R ³ may be the same or different. Among the compounds represented by the above formula (I), R ¹ ,
Compounds in which R ² and R ³ are the same or different alkyl groups are preferred, and compounds in which R ¹ is an i-propyl group and R ² and R ³ are methyl groups are more preferred. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of the compound represented by the above formula (I) include dehydroabietic acid. Such a compound represented by the above formula (I), for example, dehydroabietic acid, can be obtained by disproportionating or dehydrogenating the natural rosin and then purifying it.

The compounds represented by the above formula (I) are used alone or in combination of two or more as a crystal nucleating agent for polyolefin. The metal salt of the compound represented by the formula (I) is a compound represented by the following formula (II).

[0031]

[Chemical 4]

In the formula, R ¹ , R ² and R ³ are the same as those in the formula (I). M is a monovalent metal ion, specifically, a monovalent metal ion such as lithium, sodium, potassium, rubidium or cesium, or a divalent metal ion such as beryllium, magnesium, calcium, strontium, barium or zinc. And a trivalent metal ion such as aluminum.

Of these, monovalent or divalent metal ions are preferable, and sodium ions, potassium ions, and magnesium ions are more preferable. n is the same integer as the valence of M, and is an integer of 1 to 3.

Among the compounds represented by the above formula (II), R ¹ , R ² and R ³ are the same or different alkyl groups respectively, or M is a monovalent or divalent metal ion. Certain compounds are preferred, where R ¹ is i-
More preferred is a compound which is a propyl group and R ² and R ³ are methyl groups, or a compound where M is a sodium ion, potassium ion or magnesium ion, R ¹ is an i-propyl group, and R ² and R ^A compound in which ³ is a methyl group and M is a potassium ion or a magnesium ion is particularly preferred. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of the compound represented by the above formula (II) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, Examples include metal salts of dehydroabietic acid such as zinc dehydroabietic acid and aluminum dehydroabietic acid.

The compound represented by the above formula (II) can be produced by subjecting the carboxylic acid represented by the above formula (I) to metal chloride by a conventional method. For example, when the compound represented by the formula (II) is a metal salt of dehydroabietic acid, the metal salt is represented by the following formula (III)

[0037]

[Chemical 5]

It can be produced by reacting dehydroabietic acid represented by and the metal compound in the same manner as in the above method. The compound represented by the formula (II) is used alone or in combination of two or more as a crystal nucleating agent for polyolefin. Examples of the combination of two or more compounds include, for example, R ^{1 to} R ³ in the formula (II).
In which at least one is the same and M is different, a combination of two or more compounds in which at least one of R ^{1 to} R ³ in the formula (II) is different and M is the same And so on.

The compound [compound (I)] represented by the above formula (I) and the metal salt [compound (II)] of the compound represented by the above formula (I) are the compound (I) or The compound (II) is used alone or in combination with the compound (I) and the compound (II) as a crystal nucleating agent for polyolefin. As a combination of the compound (I) and the compound (II), it is preferable to combine the compound (I) and the compound (II) which is a metal salt of the compound (I). In addition, carboxyl group 1 of dehydroabietic acid
It is preferable to appropriately combine the metals in the range of 0.05 to 1 equivalent per equivalent.

Examples of the polyolefin to which such a crystal nucleating agent of the present invention can be added include polyethylene, polypropylene, polybutene-1, polymethylpentene, polymethylbutene and the like. Examples of the polyolefin to which the crystal nucleating agent of the present invention can be added include a composition composed of two or more kinds of polyolefins and a composition composed of 50% by weight or more of a polyolefin and less than 50% by weight of a resin other than the polyolefin. .

The crystal nucleating agent of the present invention is particularly preferably used as a crystal nucleating agent for polyethylene, polypropylene and polybutene-1. The blending ratio of the crystal nucleating agent of the present invention to the polyolefin is not particularly limited, but the polyolefin 10
It is in the range of 0.001 to 5 parts by weight, preferably 0.05 to 2 parts by weight, relative to 0 parts by weight. By blending the crystal nucleating agent in the above ratio, the crystallization rate is improved and the crystals are made finer without impairing the excellent properties originally possessed by the polyolefin, and the mechanical properties and / or
Alternatively, it is possible to produce a molded article having excellent optical characteristics, and it is economically advantageous.

The crystal nucleating agent of the present invention can improve the crystallization rate and generate fine crystals during molding. As a result, mechanical properties such as rigidity and heat resistance of polyolefin and / or optical properties such as transparency and surface smoothness are improved.

Within the scope of the object of the present invention, the crystal nucleating agent of the present invention comprises other additives such as stabilizers, weathering stabilizers, plasticizers, lubricants, antistatic agents, colorants, foaming agents, You may use together with a flame retardant, a reinforcing agent, such as a glass fiber, a filler, a filler, etc.

In order to mix the crystal nucleating agent of the present invention with the polyolefin, a conventionally known method used when blending a plasticizer, a stabilizer, a colorant, a filler and the like with the polyolefin can be adopted. For example, a mixer such as an extruder or a plastomill can be used for mixing.

The polyolefin blended with the crystal nucleating agent of the present invention is used for producing a desired molded article by various molding methods such as injection molding, extrusion molding and blow molding.

[0046]

The crystal nucleating agent for polyolefin according to the present invention improves the crystallization rate of polyolefin and makes the crystal fine. A molded product having excellent mechanical properties and / or optical properties can be produced from the polyolefin containing the crystal nucleating agent.

[0047]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

The performance as a crystal nucleating agent was evaluated by the following method. Crystallization rate: The obtained pellet was analyzed by a differential scanning calorimeter (D
The crystallization rate was evaluated by measuring the crystallization exothermic peak temperature [crystallization temperature (Tc)] after cooling from the molten state at a constant rate (10 ° C./min) by SC). Those having a high effect of increasing the crystallization temperature (Tc) have a high effect of increasing the crystallization rate.

Rigidity (FM): length 100 mm, width 10 mm, thickness 2 cut from a 2 mm thick compression molded sheet
Using a mm test piece, the flexural modulus was measured according to JIS K7203. A material having a large flexural modulus has high rigidity.

Transparency (haze): A haze according to JIS K6714 was measured using a compression molding test piece having a thickness of 1.0 mm. Those with low haze have high transparency.

[0051]

Examples 1 to 10 Polypropylene homopolymer (MFR measured at a temperature of 230 ° C. and a load of 2.16 kg: 1.2
g / 10 minutes) 100 parts by weight of Irganox 101
0.1 parts by weight of 0 ^TM (manufactured by Ciba Geigy) and 0.1 parts by weight of calcium stearate were added, and the following Table 1
Alternatively, the crystal nucleating agent shown in Table 2 was added in the amount shown in Table 3 below, and the mixture was pelletized by melt blending at a resin temperature of 230 ° C. by an extruder.

Using the pellets obtained, a melting temperature of 230
Various test pieces were prepared by compression molding and injection molding at a cooling temperature of 20 ° C. Using this test piece, various physical properties were measured by the above-mentioned test methods. The results are shown in Table 3.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

Comparative Example 1 Pellets were produced in the same manner as in Examples 1 to 10 except that the crystal nucleating agent was not used.

Using the pellets obtained, Examples 1-10
Various test pieces were prepared in the same manner as in. Using this test piece, various physical properties were measured in the same manner as in Examples 1-10. The results are shown in Table 3.

[0057]

Comparative Example 2 0.3 weight of para-t-butylaluminum benzoate (manufactured by Shell Chemical Co .: trade name ALPTBB ^™ ) (Compound H) was used in place of the crystal nucleating agent shown in Table 1 or 2 as the crystal nucleating agent. Pellets were produced in the same manner as in Examples 1 to 10 except that part was added.

Using the pellets obtained, Examples 1-10
Various test pieces were prepared in the same manner as in. Using this test piece, various physical properties were measured in the same manner as in Examples 1-10. The results are shown in Table 3.

[0059]

[Comparative Example 3] As a crystal nucleating agent, 0.3 part by weight of dibenzylidene sorbitol (manufactured by EC Chemicals: trade name EC-1 ^™ ) (Compound I) was added in place of the crystal nucleating agent shown in Table 1 or Table 2 above. Pellets were manufactured in the same manner as in Examples 1 to 10 except for the above.

Using the pellets obtained, Examples 1-10
Various test pieces were prepared in the same manner as in. Using this test piece, various physical properties were measured in the same manner as in Examples 1-10. The results are shown in Table 3.

[0061]

[Table 3]

[0062]

Examples 11 to 19 Linear low density polyethylene (temperature 1
MFR measured at 90 ° C. and a load of 2.16 kg: 2.3 g
/ 10 minutes, density at 23 ° C .: 0.920 g / cc)
To 100 parts by weight, 0.1 parts by weight of Irganox 1076 ^™ (manufactured by Ciba-Geigy) and 0.1 parts by weight of calcium stearate were added, and the crystal nucleating agent shown in Table 1 or 2 was added in the amount shown in Table 4. Then, it was melt-blended with an extruder at a resin temperature of 200 ° C. and pelletized.

Using the pellets obtained, a melting temperature of 200
Various sheets were prepared by compression molding at a temperature of 20 ° C and a cooling temperature of 20 ° C. From this sheet, various physical properties were measured by the test methods described above. The results are shown in Table 4.

[0064]

Comparative Example 4 Pellets were produced in the same manner as in Examples 11 to 19 except that the crystal nucleating agent was not used.

Using the obtained pellets, Examples 11 to 1
Various sheets were prepared in the same manner as in No. 9. Using this sheet, various physical properties were measured in the same manner as in Examples 11 to 19. The results are shown in Table 4.

[0066]

Comparative Example 5 Pellets were produced in the same manner as in Examples 11 to 19 except that 0.3 part by weight of Compound I was added as the crystal nucleating agent instead of the crystal nucleating agent shown in Table 1 or Table 2.

Using the obtained pellets, Examples 11 to 1
Various sheets were prepared in the same manner as in No. 9. Using this sheet, various physical properties were measured in the same manner as in Examples 11 to 19. The results are shown in Table 4.

[0068]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Kasaii Shi 1-2 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Mitsui Petrochemical Industries, Ltd. (72) Inventor Kimio Ueda Osaka, Osaka 1-9, Tsurumi, Tsurumi-ku, Arakawa Chemical Industry Co., Ltd. (72) Inventor Masao Maeda, 1-9, Tsurumi, Tsurumi-ku, Osaka-shi, Osaka (72) Inventor (72) Koji Yamada 1-9, Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Prefecture Arakawa Chemical Industry Co., Ltd. (56) References JP-A-58-104933 (JP, A) JP-A-59-129239 (JP, A) ) JP-A-50-26846 (JP, A) JP-A-7-330967 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (6)

(57) [Claims] 1. A crystal nucleus for a polyolefin, which contains as a main component at least one metal salt of a rosin selected from the group consisting of a metal salt of dehydroabietic acid, a metal salt of dihydroabietic acid and a metal salt of dihydropimaric acid. Agent. 2. The crystal nucleating agent for polyolefin according to claim 1, wherein the metal salt is at least one metal salt selected from the group consisting of sodium salt, potassium salt and magnesium salt. 3. A crystal nucleating agent for polyolefin, comprising a compound represented by the following formula (I) and / or a metal salt thereof; (In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group and may be the same or different). 4. The crystal nucleating agent for polyolefin according to claim 3, wherein in the formula (I), R ¹ is an isopropyl group, and R ² and R ³ are methyl groups. 5. The polyolefin according to claim 3 or 4, wherein the metal salt of the compound represented by the formula (I) is at least one metal salt selected from the group consisting of sodium salt, potassium salt and magnesium salt. Crystal nucleating agent. 6. 100 parts by weight of polyolefin and 0.00 of the crystal nucleating agent according to claim 1.
A polyolefin composition comprising 1 to 5 parts by weight.