JPH0859968A - Crystal nucleating agent for polyester - Google Patents

Abstract

(57) [Summary] [Structure] At least one abietic acid selected from a compound represented by the following formula (IA) and a metal salt thereof, and a compound represented by the following formula (IB) and a metal salt thereof. A crystal nucleating agent for polyester, characterized by comprising a compound (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). [Effect] The rate of crystallization of polyester can be improved, and a molded product having excellent mechanical properties can be obtained.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Polyesters such as polyethylene terephthalate and polybutylene terephthalate have excellent processability, chemical resistance, electrical properties, mechanical properties, etc., and are therefore injection molded products, hollow molded products, Processed into films, sheets, fibers, etc., and used for various purposes.
However, depending on the application, the rigidity and heat resistance may not be sufficient.

It is known that in order to improve the rigidity and heat resistance of a molded product made of such a polyester, the crystallization speed of the polyester can be increased and fine crystals can be rapidly produced during the molding process. . Therefore, a crystal nucleating agent such as talc has been conventionally used to accelerate the crystallization rate of polyester.

However, the conventional crystal nucleating agent is not always sufficient in improving the crystallization rate, and the mechanical properties such as rigidity and heat resistance of the resulting molded article are not always satisfactory.

JP-A-58-160343 discloses that polyethylene terephthalate or polyester containing it as a main component is added to thorium salts such as carboxylic acid metal salts of terpenes such as abietic acid, pimaric acid and neoabietic acid. A polyester composition containing a metal salt such as a potassium salt, a lithium salt, or a calcium salt is described.

However, in the polyester composition containing the carboxylic acid metal salt of a terpene as described in this publication, the crystallization rate is not sufficient,
There was a problem that the mechanical properties of the obtained molded body were not sufficient.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a polyester capable of improving the crystallization rate of polyester and obtaining a molded article having excellent mechanical properties. It is intended to provide a crystal nucleating agent for use.

[0008]

SUMMARY OF THE INVENTION The crystal nucleating agent for polyester according to the present invention is selected from the compound represented by the following formula (IA) and its metal salt, and the compound represented by the following formula (IB) and its metal salt. It is characterized by comprising at least one abietic acid compound.

[0009]

Embedded image

(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). In the present invention, in the compound represented by the formula (IA), the compound represented by the formula (IB) and metal salts thereof, R ¹ is an isopropyl group and R ² and R ³ are methyl groups. Compounds or metal salts thereof are preferred. In addition, the above formula (I
The metal salt of the compound represented by A) and the metal salt of the compound represented by (IB) are preferably at least one metal salt selected from the group consisting of sodium salt, potassium salt and magnesium salt. Further, the above formula (I
In the metal salt of the compound represented by A) and the metal salt of the compound represented by (IB), R ¹ is an isopropyl group and R ^{2 is}
More preferably, it is at least one metal salt selected from the group consisting of sodium salt, potassium salt and magnesium salt of a compound in which R ³ is a methyl group.

Since the crystal nucleating agent for polyester of the present invention improves the crystallization rate of polyester and makes the crystals finer, it is possible to obtain a molded product having excellent mechanical properties. The polyester in which the crystal nucleating agent for a polyester of the present invention is blended 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 and the like. It

[0012]

DETAILED DESCRIPTION OF THE INVENTION The crystal nucleating agent for polyester according to the present invention will be specifically described below. Compound (IA) and Compound (IB) The crystal nucleating agent for polyester according to the present invention has the following formula (I
A) a compound [compound (IA)] and a metal salt thereof, and at least one abietic acid selected from a compound [compound (IB)] and a metal salt thereof represented by the following formula (IB): It is composed of compounds.

[0013]

[Chemical 3]

In formulas (IA) and (IB), R ¹ and R ²
And R ³ is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. Specifically as an alkyl group,
Methyl, ethyl, n-propyl, i-propyl, n-butyl,
Examples thereof include alkyl groups having 1 to 8 carbon atoms such as i-butyl, tert-butyl, pentyl, heptyl and octyl, and these groups have substituents such as hydroxyl group, carboxyl group, alkoxy group and halogen. Good.

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 compound represented by the formula (IA) and the compound represented by the formula (IB), compounds in which R ¹ , R ² and R ³ are the same or different alkyl groups are preferable, and R ¹ is i More preferred is a compound that is a propyl group and R ² and R ³ are methyl groups. Such compounds are
Especially, the effect of improving the crystallization rate is excellent.

Specific examples of the compound represented by the formula (IA) include dehydroabietic acid and the like, and specific examples of the compound represented by the formula (IB) include dihydroabietic acid and the like. .

Of the compounds represented by the formula (IA) and the compound represented by the formula (IB), the dehydroabietic acid represented by the formula (IA) includes gum rosin and tall oil rosin. , Wood rosin and other natural rosins are obtained by disproportionation or dehydrogenation and subsequent purification. The natural rosin includes pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid,
A plurality of resin acids such as dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid are usually contained.

Compound (IIA) and Compound (IIB) The metal salt of the compound represented by the above formula (IA) is a compound [compound (IIA)] represented by the following formula (IIA):
The metal salt of the compound represented by the formula (IB) is a compound represented by the following formula (IIB) [compound (IIB)].

[0021]

[Chemical 4]

[0022]

[Chemical 5]

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

Of these, M is preferably a monovalent or divalent metal ion, more preferably sodium ion, potassium ion, or magnesium ion.

N is the same integer as the valence of the metal ion M, and is an integer of 1 to 3. Among the compounds represented by the formulas (IIA) and (IIB), compounds in which R ¹ , R ² and R ³ are the same or different alkyl groups, or M is a monovalent or divalent metal ion And R ¹ is an i-propyl group, R ²
And a compound in which R ³ is a methyl group, or a compound in which M is a sodium ion, a potassium ion or a magnesium ion, R ¹ is an i-propyl group, R ² and R ³ are methyl groups, Further, a compound in which M is sodium ion, potassium ion or 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 formula (IIA) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, and Examples thereof include metal salts of dehydroabietic acid such as zinc dehydroabietic acid and aluminum dehydroabietic acid, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferably used.

Specific examples of the compound represented by the formula (IIB) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, Examples thereof include metal salts of dihydroabietic acid such as zinc dihydroabietic acid and aluminum dihydroabietic acid, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferably used. Such a formula (IIA)
The compound represented by and the compound represented by the formula (IIB) are used alone or in combination of two or more as a crystal nucleating agent for polyester.

Preparation of Compound (IIA) and Compound (IIB)
Described manufacturing method forming compound (IIA) as an example. The metal salt represented by the formula (IIA) has the formula (I
It can be produced by reacting the carboxylic acid represented by A) with a metal compound by a conventional method to give a metal salt.

Explaining in more detail below, examples of the above metal compounds include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides of metals such as sodium, potassium and magnesium. And so on.

Such a metal compound and the above formula (IA)
In order to produce a compound (IIA), which is a metal salt of the compound represented by the formula (IA), by reacting with a compound represented by A method of directly reacting the compound represented by (IA) with the metal compound in the presence or absence of an organic solvent (direct method) (2) Metal salt of the compound represented by formula (IA) and the metal compound Examples of the method include a method (metalysis method) in which salt is subjected to a salt exchange by reacting with water and / or in the presence of an organic solvent.

When the direct method (1) is adopted, considering the yield and workability, the compound represented by the formula (IA) is dissolved in an organic solvent and reacted with the metal compound in a solution state. Preferably.

For example, when the metal salt of dehydroabietic acid is described as an example, the metal salt of dehydroabietic acid has the following formula (IIIA).

[0033]

[Chemical 6]

It can be produced by the above-mentioned direct method (1) in which dehydroabietic acid represented by the following is dissolved in an organic solvent and reacted with the metal compound in a solution state. Examples of the organic solvent used in the direct method (1) or the metathesis method (2) include, for example, aromatic hydrocarbon solvents such as toluene and xylene, ethyl acetate, ester solvents such as butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. And a ketone solvent. This organic solvent is used in consideration of solubility with respect to the compound represented by the formula (IA), water separability, and the like.

The amount of the organic solvent used in reacting the compound represented by the formula (IA) with the metal compound is not particularly limited, but the amount of the compound represented by the formula (IA) is usually 100 parts by weight. On the other hand, it is about 20 to 500 parts by weight.
The reaction temperature is not particularly limited, but is usually 40 to 15
The temperature is about 0 ° C., preferably 50 to 120 ° C. In the reaction of the compound represented by the formula (IA) with the metal compound, the amount of the metal introduced to the carboxyl group of the compound represented by the formula (IA) is usually 5 to 100 equivalent%, preferably 10 to 1
It is carried out so that the amount becomes 00 equivalent%. After completion of the reaction, the organic solvent is distilled off to obtain the desired metal salt of the compound represented by the formula (IA). In addition, the obtained formula (IA)
The metal salt of the compound represented by may be purified if necessary.

When the metathesis method (2) is adopted, a metal salt (for example, an alkali metal salt) of the compound represented by the formula (IA) is dissolved in an organic solvent in consideration of yield and workability. However, it is preferable to react with a different metal compound in the presence of water. 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 the compound represented by the formula (IA) in the metal salt and the water separability.

The amount of the organic solvent used in reacting the metal salt of the compound represented by the formula (IA) with the metal compound is not particularly limited, but is usually the metal salt of the compound represented by the formula (IA). The amount is about 100 to 1000 parts by weight based on 100 parts by weight. The reaction temperature is not particularly limited, but is usually about 40 to 150 ° C, preferably 50 to 90 ° C.
Range. After completion of the reaction, the organic solvent and water are distilled off to obtain the desired metal salt of the compound represented by the formula (IA), that is, the compound (IIA). The obtained metal salt of the compound represented by the formula (IA) may be purified if necessary.

The compound (IIA) thus obtained, which is a metal salt of the compound represented by the formula (IA), is preferably made into fine particles and used as a crystal nucleating agent. Formula (IA)
By finely dividing the metal salt of the compound represented by the formula (3) into a polyester such as polyethylene terephthalate, the metal salt of the compound represented by the formula (IA) can be uniformly dispersed in the polyester. it can.

As a method for forming fine particles of the metal salt of the compound represented by formula (IA), a conventionally known method can be adopted,
For example, (a) a method of pulverizing the obtained solid product of a metal salt of a compound represented by the formula (IA) by a wet or dry method (b) a compound represented by the formula (IA) and the metal compound After completion of the reaction of, without distilling off the organic solvent, water in a solution state and, if necessary, a surfactant and / or a water-soluble polymer are added, and then emulsified and dispersed,
Examples include a method of distilling off water and an organic solvent.

As the surfactant and / or water-soluble polymer used in the above-mentioned method (b), conventionally known ones 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), water and an organic solvent are distilled off, followed by washing with water to remove the surfactant and water-soluble polymer from the metal salt of the compound represented by the formula (IA). Good.

The production method has been described above by taking the metal salt of the compound represented by the formula (IA) [compound (IIA)] as an example. The metal salt of the compound represented by the formula (IB) [compound (IIB) )] Can also be produced in the same manner as the metal salt (IIA).

In the present invention, the above compound (IA),
Compound (IIA), compound (IB) and compound (IIB)
Can be used alone or in combination of two or more.
Used as crystal nucleating agent for stealth. In the above formula (IIA)
As a combination of two or more compounds represented,
For example, in the above formula (IIA), R¹~ R³Are the same,
A combination of two or more compounds having different Ms,
R in formula (IIA) ¹~ R³At least one of is different
Or combining two or more compounds with the same M
And the like.

As the combination of the compound (IA) and the compound (IIA), the compound (IA) and this compound (I
It is preferable to combine with the compound (IIA) which is a metal salt of A). Further, it is preferable to appropriately combine metals in an amount of 0.05 to 1 equivalent per equivalent of the carboxyl group of dehydroabietic acid.

Examples of the combination of two or more compounds represented by the formula (IIB) include the same ones as described above, and the same combinations as above are preferable. Examples of the polyester to which the crystal nucleating agent of the present invention can be added include aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, as well as polycaprolactone and polyhydroxybutyrate.

The polyester to which the crystal nucleating agent of the present invention may be added may contain a resin other than polyester in an amount of less than 50% by weight. Examples of such resins other than polyester include polyolefin, polyamide, and polycarbonate.

The crystal nucleating agent of the present invention is particularly preferably used as a crystal nucleating agent for polyethylene terephthalate.
The compounding ratio of the crystal nucleating agent of the present invention to the polyester is not particularly limited, but it is 0.
001 to 5 parts by weight, preferably 0.05 to 2 parts by weight. By blending the crystal nucleating agent in the above proportion, the excellent properties inherent to the polyester are not impaired, the crystallization speed is improved, and the crystals are refined to produce a molded product having excellent mechanical properties. It is possible and economically advantageous.

The crystal nucleating agent of the present invention can improve the crystallization rate and generate fine crystals during molding. As a result, properties such as mechanical properties such as rigidity and heat resistance of polyester 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 polyester, a conventionally known method used when blending a plasticizer, a stabilizer, a coloring agent, a filler and the like with the polyester can be adopted. For example, a mixer such as an extruder or a plastomill can be used for mixing.

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

[0051]

Industrial Applicability The crystal nucleating agent for polyester according to the present invention improves the crystallization rate of polyester and makes the crystals finer. A molded product having excellent mechanical properties can be produced from the polyester containing the crystal nucleating agent.

[0052]

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)] by cooling at a constant rate (10 ° C./minute) from the molten state 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.

[0055]

Examples 1 to 7 To 100 parts by weight of a polyethylene terephthalate resin (J125 manufactured by Mitsui Pet Resin Co., Ltd.), a crystal nucleating agent shown in Table 1 below was added in an amount shown in Table 2 below.
The resin was melt-blended and pelletized at a resin temperature of 280 ° C. by an extruder.

Using the pellets obtained, a melting temperature of 280
Various test pieces were prepared by compression molding at 20 ° C and 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 2.

[0058]

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

Using the pellets thus obtained, various test pieces were prepared in the same manner as in Example 1. Using this test piece, various physical properties were measured in the same manner as in Example 1. Table 2 shows the results.

[0060]

Comparative Example 2 Pellets were produced in the same manner as in Example 1 except that the crystal nucleating agent G shown in Table 1 was used.

Using the pellets thus obtained, various test pieces were prepared in the same manner as in Example 1. Using this test piece, various physical properties were measured in the same manner as in Example 1. Table 2 shows the results.

[0062]

[Table 1]

[0063]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toru Kasai Toshi Shi, 1-2-6, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., 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, Osaka (72) Inventor Hiroshi Matsumoto 1-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Arakawa Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A compound represented by the following formula (IA) and a metal salt thereof, and at least one abietic acid compound selected from the compound represented by the following formula (IB) and a metal salt thereof. A crystal nucleating agent for polyester characterized by the following; (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). 2. The crystal nucleating agent for polyester according to claim 1, wherein in each of the formula (IA) and the formula (IB), R ¹ is an isopropyl group and R ² and R ³ are methyl groups. . 3. The metal salt of the compound represented by formula (IA) and the metal salt of the compound represented by (IB) are both at least one selected from the group consisting of sodium salt, potassium salt and magnesium salt. It is a metal salt.
Alternatively, the crystal nucleating agent for polyester according to the item 2.