JP2018123191A - Ethylene furanoate-based polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene furanoate-based polyester resin composition that uses an ethylene furanoate-based polyester, which can be produced only from biomass, without modification, with its moldability effectively improved.SOLUTION: A resin composition contains an ethylene furanoate-based polyester as a main polymer component (A), and contains, as a sub-polymer component (B), at least one selected from the group consisting of an ethylene-(meth) acrylic acid copolymer-based ionomer (B1), polybutylene succinate (B2) and a reactive compound-containing non-crystalline polyester (B3).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing ethylene furanoate-based polyester as a main component, and more particularly to an ethylene furanoate-based polyester resin composition with improved stretch moldability.

  Ethylene furanoate-based polyester is a polymer obtained by polymerization of furandicarboxylic acid produced from bio-derived saccharide raw materials and bio-derived ethylene glycol, and does not use fossil resources. It is known as a resin that can be synthesized.

Such an ethylene furanoate polyester (hereinafter sometimes referred to as PEF) has not only transparency equivalent to that of polyethylene terephthalate (PET), but also extremely high gas barrier properties compared to PET. (Oxygen barrier property is about 10 times and water vapor barrier property is about twice), and practical application to various applications is being studied.
For example, Patent Document 1 proposes a container preform formed using a PEF copolymer in which pyromellitic dianhydride or pentaerythritol is incorporated in a chain structure, and a container obtained from the preform. ing.

Special table 2016-531186

  However, as can be understood from the above-mentioned Patent Document 1 in which a preform or the like is molded using a PEF copolymer, the ethylene furanoate-based polyester (PEF) has excellent strength characteristics. For example, there has been a drawback that a high processing stress is required when performing stretch molding. It is considered that such disadvantages can be improved by introducing copolymerized units into PEF. However, the introduction of copolymerized units not only impairs the advantage of PEF of 100% biomass, but also significantly increases the PEF production process. Will bring about changes.

  Accordingly, an object of the present invention is to provide an ethylene furanoate-based polyester resin composition in which an ethylene furanoate-based polyester that can be produced with 100% biomass is used as it is and its moldability is effectively improved.

According to the present invention, the main polymer component (A) includes an ethylene furanoate-based polyester,
At least selected from the group consisting of ethylene- (meth) acrylic acid copolymer ionomer (B1), polybutylene succinate (B2) and reactive compound-containing amorphous polyester (B3) as the secondary polymer component (B) A resin composition characterized by containing 1 type is provided.
The resin composition of the present invention is used as a stretch-molded product by stretch molding using the resin composition.

In the resin composition of the present invention,
(1) The subpolymer component (B) is contained in an amount of 5 to 40 parts by mass per 100 parts by mass of the main polymer component (A).
Is preferred.

  The resin composition of the present invention contains an ethylene furanoate-based polyester as the main polymer component (A), but the ethylene- (meth) acrylic acid copolymer ionomer (for the main polymer component (A) ( An important feature is that at least one selected from B1), polybutylene succinate (B2) and reactive compound-containing amorphous polyester (B3) is blended as a subpolymer component (B). Such a subpolymer component (B) functions as a modifier that improves the moldability of the ethylene furanoate-based polyester.

That is, as shown in Examples described later, when a dumbbell tensile test is performed on a test piece obtained by injection molding using ethylene furanoate polyester, the maximum stress is a large value of 101.7 MPa. (Comparative Example 1), according to the present invention, the subpolymer (B1), (B2), (B3) or the subpolymer component (B) as described above is blended with the ethylene furanoate polyester. When the same tensile test is performed using the obtained resin composition, the maximum stress decreases by about 15 to 30%.
As understood from this, the resin composition of the present invention can be molded with a lower processing stress than the ethylene furanoate polyester alone, and as a result, there is no inconvenience such as molding failure. It becomes possible to perform stretch molding. Thus, according to the present invention, the stretch formability of the ethylene furanoate-based polyester is greatly improved.

<Main polymer component (A)>
In the present invention, the ethylene furanoate-based polyester (PEF) used as the main polymer component (A) has a structure represented by the following formula.
In the formula, n is a positive integer.

  That is, as described above, this PEF is obtained by ester polymerization of furandicarboxylic acid and ethylene glycol, and both furancarboxylic acid and ethylene glycol are raw materials that can be obtained from biotechnology. .

In the present invention, in principle, the PEF having the above structure has a small amount of copolymerized units (for example, polyhydric alcohols and polybasic acids within the range in which transparency and gas barrier properties are not impaired. ) May be introduced, but the introduction of such a comonomer unit impairs the original excellent properties of PEF. Therefore, in order to make the most of the advantages of the present invention, it is preferable to use 100% bio-derived PEF into which such copolymerized units are not introduced as the main polymer component (A).
Such a PEF may have a molecular weight sufficient to form a film, but from the viewpoint of moldability and the like, the weight average molecular weight is usually in the range of about 10,000 to 100,000. Is preferred.

<Sub-polymer component (B)>
In the present invention, ethylene- (meth) acrylic acid copolymer ionomer (B1), polybutylene succinate (B2) and reactive compound are used to improve the moldability of PEF used as the main polymer (A). At least one of the containing amorphous polyester (B3) is used as the secondary polymer component (B). These sub-polymer components (B) are all excellent in affinity with PEF and can be uniformly dispersed, thereby enabling molding with low stress.

Minor polymer component (B1);
The ethylene- (meth) acrylic acid copolymer system ionomer (B1) has a structure in which the molecules of a copolymer of ethylene and methacrylic acid or acrylic acid are cross-linked with a metal ion. Examples thereof include alkali metal ions such as ions and K ions, Zn ions and Al ions.
Such an ionomer (B1) is usually prepared by producing a copolymer of ethylene and (meth) acrylic acid (usually containing 1 to 30 mol% of carboxylic acid units), and then partially or entirely carboxylic acid. Other vinyl monomers may be copolymerized as long as they are produced by neutralization with ions and a certain amount of carboxylic acid units are retained. Such an ionomer (B1) is commercially available, for example, under the trade name of High Milan from Mitsui DuPont Polychemical Co., Ltd., and an ionomer of an ethylene-methacrylic acid copolymer is particularly suitable.

Minor polymer component (B2);
The polybutylene succinate (B2) is a polyester of succinic acid and 1,4-butanediol, and generally has a weight average molecular weight of about 50,000 to 400,000. Like PEF, it can also be produced from bio-derived raw materials. Such polybutylene succinate (B2) is commercially available, for example, from Mitsubishi Chemical Corporation under the name Bio PBS.

Minor polymer component (B3);
Furthermore, the reactive compound-containing amorphous polyester (B3) includes an amorphous polyester and a reactive compound.

  This non-crystalline polyester is a so-called copolymer polyester, for example, an aromatic dicarboxylic acid having 8 to 14 carbon atoms represented by terephthalic acid or isophthalic acid, and ethylene glycol, diethylene glycol, propanediol, or cyclohexanediol. A polyfunctional compound containing 3 or more ester-forming functional groups such as trimellitic acid, pyromellitic acid, and glycerin, if necessary. It is a copolyester containing ester units introduced by use, and generally has a reduced viscosity of 0.4 to 1.50 dl / g.

The reactive compound is a vinyl copolymer or epoxy compound having a functional group reactive with an ester, and usually has a weight average molecular weight of 200 to 500,000, particularly 7000 to 40,000.
Typical functional groups reactive with esters include glycidyl groups, isocyanate groups, carboxyl groups, carboxylate metal bases, ester groups, hydroxyl groups, amino groups, carbodiimide groups, etc., and glycidyl groups are particularly preferred. .
In such a reactive compound, examples of the vinyl-based copolymer include a copolymer containing a vinyl aromatic unit such as styrene, a glycidylalkyl (meth) acrylate unit, and an alkyl (meth) acrylate unit as necessary, for example, A styrene / methyl methacrylate / glycidyl methacrylate copolymer can be exemplified. Examples of the epoxy compound include bisphenol A type, cresol novolac type, and phenol novolac type epoxy compounds.
Such reactive compounds are generally included in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the amorphous polyester.

  The above-mentioned reactive compound-containing non-crystalline polyester (B3) is known from Japanese Patent No. 396998 and is commercially available from Toyobo Co., Ltd. under the trade name Byron RF.

  The above-mentioned various subpolymer components (B1) to (B3) are used alone or in combination of two or more, but such subpolymer components (B) are used in terms of ensuring good moldability. Although it varies depending on the type, it is usually preferred to be used in an amount of 5 to 40 parts by mass, particularly 10 to 30 parts by mass, per 100 parts by mass of the PEF (main polymer component (A)). That is, if this amount is small, the improvement of the moldability of the target PEF is unsatisfactory, and if it is used excessively, it is not possible to improve the moldability further, and the PEF has excellent gas barrier properties and transparency. The characteristics may be impaired.

The various subpolymer components (B1) to (B3) described above have different characteristics.
For example, in the tensile test described later, ionomer (B1) and polybutylene succinate (B2) are preferable in that the maximum stress is greatly reduced and the stretch moldability of PEF is greatly improved. In particular, ionomer (B1) ) Is optimal.
Moreover, the reactive compound containing amorphous polyester (B3) is suitable at the point which has little influence on the transparency which PEF has, and maintains the transparency.
Furthermore, from the viewpoint of biomass, polybutylene succinate (B2) is suitable, and this subpolymer component (B2) is optimal in order to maximize the advantage of PEF of 100% biomass.
Furthermore, ionomer (B1) and polybutylene succinate (B2) are preferable in terms of applicability to food containers and the like, and ionomer (B1) is particularly optimal.
As described above, the subpolymer components (B1) to (B3) described above are subpolymers that are PEF modifiers in consideration of the properties of the molded product obtained from the resin composition. Used as (B).

<Other ingredients>
In the resin composition of the present invention containing the above-mentioned PEF as the main polymer component (A) and the modifying sub-polymer component (B), molding with the sub-polymer (B) without impairing the excellent properties of PEF. Other resins such as PET may be blended in an appropriate amount within a range not impairing the property improving effect, and various known compounding agents such as lubricants, pigments, antioxidants, surfactants, ultraviolet rays An absorbent or the like may be blended.

<Application>
The above-described resin composition of the present invention has improved moldability of PEF, and molding defects during stretch molding are effectively suppressed. Applicable for use.

For example, using the resin composition of the present invention, a film can be formed by extrusion molding or the like, and then stretched to be used as a stretched film. Also, tube-shaped, sheet-shaped, or test-tube shaped preforms are formed by extrusion molding, injection molding, compression molding, etc., and direct blow molding, plug assist molding, biaxial stretch blowing are performed according to the preform shape. It is molded and used as a bottle-shaped, tray-shaped or cup-shaped stretched molded body.
Such a stretch-molded body is particularly suitably used as a container in the packaging field.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples as long as the structural requirements are satisfied.
The materials used in the experiment and various measurement methods are as follows.

<Material>
(1) Main polymer component (A):
Polyethylene furanoate (PEF) resin (A90A: manufactured by Avantium)
(2) Subpolymer component (B) (modifier):
Secondary polymer (B1);
Ethylene- (meth) acrylic acid copolymer ionomer
High Milan 1706: Mitsui DuPont Polychemical Co., Ltd. subsidiary polymer (B2);
Polybutylene succinate (FZ71PM: manufactured by Mitsubishi Chemical Corporation)
Secondary polymer (B3);
Reactive compound-containing amorphous polyester resin
(Byron RF100-C01: manufactured by Toyobo Co., Ltd.)

<Injection molding>
Dry PEF resin or a dry blend of PEF resin and secondary polymer mixed at a specified ratio is supplied to the hopper of an injection molding machine (NN75JS: Niigata Steel Co., Ltd.), and the barrel set temperature is 250 ° C. A dumbbell-shaped test piece (JIS K 7139, type A1) was injection molded.
<Tensile test>
Using a tensile tester (Tensilon UCT-5T: manufactured by Orientec), the initial distance between chucks is set to 80 mm, the tensile speed is set to 20 mm / min, and the tensile test of the dumbbell-shaped test piece at a test temperature of 25 ° C. The maximum value of the stress-strain curve was taken as the maximum stress (MPa).

<Example 1>
25 parts by mass of ethylene- (meth) acrylic acid copolymer ionomer (subpolymer (B1)) is dry blended with respect to 100 parts by mass of the PEF resin as the main polymer component (A), and this resin composition is used. Injection molding was performed by the method described above, a dumbbell-shaped test piece was molded, and a tensile test was performed. The maximum stress is shown in Table 1. In addition, the test sample was made into seven pieces, the maximum stress was measured about each sample, and the average value was shown in Table 1.

<Examples 2 and 3>
The same method as in Example 1 except that polybutylene succinate (subpolymer (B2)) and reactive compound-containing amorphous polyester resin (subpolymer (B3)) were used as the subpolymer (B). Were subjected to injection molding and a tensile test, the maximum stress was measured, and the results are shown in Table 1.

<Comparative Example 1>
Except that the subpolymer component (B) was not used and only the PEF resin was used, injection molding and a tensile test were performed in the same manner as in Example 1, the maximum stress was determined, and the results are shown in Table 1.

Claims (3)

Including ethylene furanoate-based polyester as the main polymer component (A),
At least selected from the group consisting of ethylene- (meth) acrylic acid copolymer ionomer (B1), polybutylene succinate (B2) and reactive compound-containing amorphous polyester (B3) as the secondary polymer component (B) 1 type of resin composition characterized by the above-mentioned.   The resin composition of Claim 1 which contains the said subpolymer component (B) in the quantity of 5-40 mass parts per 100 mass parts of said main polymer components (A).   A stretch molded article comprising the resin composition according to claim 1.