JP5147372B2 - Ionomer resin composition - Google Patents

Description

  The present invention relates to an ionomer resin composition excellent in transparency and mechanical strength suitable for molded articles such as automobile parts and sheets.

  The ionomer resin is a resin having a special structure in which the molecules of ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc, and heat sealability, It is a resin with excellent transparency, toughness, wear resistance, low temperature resistance, etc.

  In order to improve the performance of this ionomer resin, various resin compositions containing olefinic thermoplastic elastomers have been developed in the past, and resin compositions with various properties such as scratch resistance, flexibility and heat distortion resistance. It is suitably used for applications such as automobile parts, golf balls, shoe soles and seats. However, depending on the application field of the ionomer resin, a resin composition having further improved mechanical properties (hardness, bending rigidity, tensile strength at break, elongation at break, etc.) while maintaining high transparency, which is an excellent characteristic of the ionomer resin. It was desired to develop.

  The present invention has been made to solve the above-described problems, and provides a resin composition excellent in transparency and mechanical properties (hardness, bending rigidity, tensile strength at break, elongation at break, etc.). Is an issue.

  As a result of researches to solve the above-mentioned problems, the present inventor, by blending a specific thermoplastic polyamide elastomer into the ionomer resin, does not impair the characteristics such as excellent processability and transparency of the ionomer resin. The present invention was completed by finding that a resin composition excellent in mechanical properties was obtained.

That is, the present invention includes the following matters.
[1] and the ionomer resin (A) 100 parts by weight of, (b2) by copolymerization of Po Li amide oligomer and a polyester component obtained, at least a portion of the end group reaction stopped so as to have an amino group and / or hydroxyl An ionomer resin composition comprising 1 to 20 parts by weight of a thermoplastic polyamide elastomer (B) made of the prepared polyesteramide block copolymer.
[2] The ionomer resin composition according to [1], wherein the ionomer resin (A) is an ionomer of an ethylene / unsaturated carboxylic acid copolymer.
[3] A molded article formed from the ionomer resin composition according to [1] or [2].

  The ionomer resin composition of the present invention has excellent transparency and excellent mechanical properties (hardness, bending stiffness, tensile strength at break, elongation at break), and is suitable for molded parts such as automobile parts and sheets. Preferably used.

[Ionomer resin (A)]
The ionomer resin (A) used in the present invention is obtained by using an ethylene / unsaturated carboxylic acid copolymer as a base polymer and neutralizing it with a metal (ion). As the base polymer of the ionomer resin (A) used in the invention, an ethylene / unsaturated carboxylic acid copolymer is preferably used. The ethylene / unsaturated carboxylic acid copolymer has an unsaturated carboxylic acid content of 1 to 30% by weight, preferably 2 to 20% by weight, more preferably 2 to 15% by weight from the viewpoint of the balance between transparency and mechanical properties. % Of copolymer is preferably used. Such a copolymer may be not only a binary copolymer of ethylene and an unsaturated carboxylic acid but also a terpolymer obtained by arbitrarily copolymerizing other monomers. However, those containing many other monomers are generally flexible and have a low melting point, which may impair the scratch resistance and heat distortion resistance of the composition, so when using a terpolymer, for example, It is desirable to use other monomers having a content of 30% by weight or less, particularly 20% by weight or less. Such a copolymer serving as a base polymer can be obtained by radical copolymerization of ethylene and an unsaturated carboxylic acid under high temperature and high pressure.

  Examples of the unsaturated carboxylic acid in the copolymer include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, and maleic anhydride, with acrylic acid or methacrylic acid being particularly preferred.

  Examples of the other monomer include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, Examples thereof include unsaturated carboxylic acid esters such as -2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, dimethyl maleate and diethyl maleate, and carbon monoxide. Of these monomers, unsaturated carboxylic acid esters, particularly esters of acrylic acid or methacrylic acid are preferred.

  The ethylene / unsaturated carboxylic acid copolymer of the base polymer has a melt flow rate at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) of 1 to 1000 g / 10 minutes, particularly about 2 to 800 g / 10 minutes. It is desirable to use

In the present invention, as the ionomer resin (A), 10% or more, preferably 30 to 90%, more preferably 50 to 80% of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer as the base polymer is a metal ion. Used neutralized. Examples of metal ions include monovalent metal ions such as lithium, sodium, and potassium, magnesium,
Examples thereof include ions of an alkaline earth metal such as calcium or a divalent metal ion such as zinc, preferably a divalent metal ion, particularly preferably a zinc ion. These ionomer resins can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with an oxide, hydroxide, carbonate or the like of the above metal.

In view of processability and mechanical strength, the ionomer resin has a melt flow rate at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) of 0.01 to 500 g / 10 min, particularly 0.1 to 0.1 g. It is preferable to use the one of about 300 g / 10 minutes.
[Thermoplastic polyamide elastomer (B)]
Thermoplastic polyamide elastomer (B) used in the present invention is, (b2) obtained by copolymerization of Po Li amide oligomer and a polyester component, such that at least a portion of the end group having an amino group and / or hydroxyl reactive It is a thermoplastic polyamide elastomer comprising a terminated polyesteramide block copolymer. In the present invention, an ionomer resin composition having high transparency and high mechanical properties can be obtained by using the thermoplastic polyamide elastomer.

  Further, the thermoplastic polyamide elastomer (B) used in the present invention comprises a polyether ester amide block copolymer and / or a polyester amide block copolymer, and at least a part (part or all) of the block copolymer. ) Has an amino group and / or a hydroxyl group at the terminal.

Hereinafter, the polyether ester amide block copolymer and the polyester amide block copolymer will be described respectively.
Polyetheresteramide block copolymer The polyetheresteramide block copolymer is obtained by copolymerization of a polyamide oligomer and an etherester component.

<Polyamide oligomer>
As the polyamide oligomer, those which have been stopped so that at least a part of the terminal groups have an amino group and / or a hydroxyl group are used.

  The polyamide oligomer includes (1) an aminocarboxylic acid having 6 or more carbon atoms, (2) a lactam having 6 or more carbon atoms, (3) a diamine having 2 to 12 carbon atoms, and (4) an aliphatic having 6 to 22 carbon atoms, Among the alicyclic or aromatic dicarboxylic acids and their ester derivatives and (5) high-purity polymerized fatty acids containing 93% or more of dimer acids (dimerized fatty acids) having 20 to 48 carbon atoms and their ester derivatives It is obtained by a polyamidation reaction using at least one selected polyamide-forming monomer.

Examples of polyamide-forming monomers are given below.
(1) Examples of aminocarboxylic acids having 6 or more carbon atoms include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
(2) Examples of lactams having 6 or more carbon atoms include ω-caprolactam, enantolactam, capryllactam, lauryllactam, ω-laurolactam, and the like. (3) Examples of diamines having 2 to 12 carbon atoms include ethylene diamine, hexamethylene diamine, tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4 (or 2,4,4). 4) Aliphatic diamines such as -trimethylhexamethylenediamine, alicyclic and aromatic diamines such as bis- (4,4'-aminocyclohexyl) methane, metaxylylenediamine, and paraxylylenediamine.
(4) C6-C22 aliphatic, alicyclic or aromatic dicarboxylic acids and ester derivatives thereof include, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecane Dionic acid, eicosandioic acid, eicosadienedioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, xylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and their ester derivatives Etc.
(5) As a polymerized fatty acid and a derivative thereof mainly composed of a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms, one having at least one double bond or triple bond having 10 to 24 carbon atoms. Examples include polymerized fatty acids obtained by polymerizing basic unsaturated fatty acids. Specific examples include natural animal vegetable oil fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, polymerized fatty acids polymerized from oleic acid, linoleic acid, erucic acid and the like obtained by purifying them, and ester derivatives thereof.

  Commercially available polymerized fatty acids usually contain dimer acid (dimerized fatty acid) as the main component, but also contain fatty acids as raw materials and fatty acids higher than trimer, but dimer acid (dimerized fatty acid). Those having a content of 70% or more, preferably those having a dimer acid content of 93% or more, and having lowered the degree of unsaturation by hydrogenation are preferred. In particular, commercially available products such as Prepol 1009, Prepol 1010 (manufactured by Unikema) and Empor 1010 (Henkel) are preferable. Of course, mixtures and ester derivatives thereof may be used.

<Ether ester component>
The ether ester component has high purity containing 93% or more of i) aliphatic, alicyclic or aromatic dicarboxylic acid having 6 to 12 carbon atoms, and ii) dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms. Polymerized fatty acid, and iii) at least one selected from these ester derivatives
One or more, and iv) the number average molecular weight is in the range of 800 to 3,000,
(I) a polyoxyalkylene glycol, (II) an aromatic ring-containing polyether diol, and (III) at least selected from a mixture of the component (I) and / or (II) and an α, ω-dihydroxy hydrocarbon It is obtained by an esterification reaction with one or more kinds.

Examples of the ether ester component are given below.
The ether ester component is an esterification of polyoxyalkylene glycol and / or aromatic ring-containing polyether diol, or a mixture thereof with α, ω-dihydroxy hydrocarbon, and the defined dicarboxylic acid and / or ester derivative thereof. Specific examples of the raw material obtained by the reaction include the following compounds.
Examples of (I) polyoxyalkylene glycol and (II) aromatic ring-containing polyether diol include, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, block or random of ethylene oxide and propylene oxide Copolymer, block or random copolymer of ethylene oxide and tetrahydrofuran, and copolymer of dihydric phenol compound and polyoxyalkylene glycol or dihydric phenol and alkylene oxide having 2 to 4 carbon atoms such as ethylene Examples thereof include oxides, propylene oxide, 1,2- or 1,4-butylene oxide, and adducts with a mixture of two or more of these.
Examples of the α, ω-dihydroxy hydrocarbon used in combination with the polyoxyalkylene glycol (III) and / or the aromatic ring-containing polyether diol of (III) include, for example, polymerization of olefin and butadiene to hydroxylate the terminal and the double bond thereof. Examples thereof include polyolefin glycol obtained by hydrogenation and hydrogenated polybutadiene glycol.

  These polyoxyalkylene glycols and / or aromatic ring-containing polyether diols and α, ω-dihydroxy hydrocarbons preferably have a number average molecular weight in the range of 800 to 3,000. More specifically, those having a number average molecular weight in the range of 1000 to 2000 are more preferably used. When the number average molecular weight is 800 or less, the solvent crack resistance is poor, and when the number average molecular weight is 3000 or more, the compatibility with the polyamide oligomer is poor and a good block copolymer cannot be obtained.

The above i) to iii) are high purity containing 93% or more of aliphatic, alicyclic or aromatic dicarboxylic acids having 6 to 12 carbon atoms and dimer acids (dimerized fatty acids) having 20 to 48 carbon atoms. Polymerized fatty acids and their ester derivatives are preferred, and specifically, one or a mixture of two or more selected from the compounds exemplified as the raw material of the above-mentioned polyamide-forming monomer is preferably used. In particular, azelaic acid, sebacic acid, dodecanedioic acid, polymerized fatty acid, terephthalic acid, and isophthalic acid are polymerizable and thermoplastic polyamide elastomer resin composition properties and chemical resistance, especially water resistance (hydrolysis resistance), solvent resistance It is preferably used from the point of crack property.

Polyesteramide block copolymer The polyesteramide block copolymer is obtained by copolymerization of a polyamide oligomer and a polyester component.

As the polyamide oligomer, the compounds exemplified for the polyamide oligomer for the polyether ester amide block copolymer described above are preferably used.
<Polyester component>
The polyester component is a compound having a repeating unit represented by the following general formula (1) and having a number average molecular weight of 800 to 3,000.

(In formula (1), R ₁ represents a residue of a diol selected from one or a mixture of two or more substituted or unsubstituted aliphatic or alicyclic diols having 2 to 54 carbon atoms. R ₂ Has 6 carbon atoms
It contains 93% or more of a dicarboxylic acid residue and / or a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms selected from one or a mixture of two or more aliphatic or aromatic dicarboxylic acids having -22. It represents a residue of a polymerized fatty acid selected from high-purity polymerized fatty acids and one or a mixture of two or more of these derivatives. )
The polyester component is obtained by an esterification reaction of a diol compound, a dicarboxylic acid, and an ester derivative thereof.

  The diol compound is preferably a substituted or unsubstituted aliphatic or alicyclic diol compound having 2 to 54 carbon atoms, specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1 , 3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3- Pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1, -Aliphatic polyhydric alcohols such as propanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclopentadiene-1,2-diol, cyclohexane-1, Examples thereof include alicyclic polyhydric alcohols such as 3-diol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol, dimer diol obtained by reducing dimer acid (dimerized fatty acid), and the like. Or it may be a mixture of two or more. In particular, one or a mixture of two or more selected from ethylene glycol, 1,4-butanediol, neopentyl glycol, dimer diol and the like is preferably used. Examples of the dimer diol that is a derivative of a polymerized fatty acid that is particularly preferably used include commercially available products such as Pripol 2033 (manufactured by Unikema), Speziol C36 / 2 (manufactured by Cognis), and Vespol HP-1000 (manufactured by Toagosei).

  As the dicarboxylic acid and ester derivative, polymerization mainly comprising an aliphatic or aromatic dicarboxylic acid having 6 to 22 carbon atoms and / or an ester derivative thereof, or a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms. Fatty acids and / or derivatives thereof are preferred. Specifically, at the polyamide-forming monomer for the polyamide oligomer, one or a mixture of two or more selected from the compounds exemplified as the starting dicarboxylic acid and ester derivatives is preferably used. It is done.

  As the polyester component, a polymerized fatty acid mainly composed of a substituted or unsubstituted aliphatic diol and / or alicyclic diol having 2 to 12 carbon atoms and a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms. And / or a polyester component made from an ester derivative thereof, or an aliphatic or aromatic dicarboxylic acid having 6 to 22 carbon atoms and / or an ester derivative thereof, and a dimer acid (dimer) having 20 to 48 carbon atoms A polyester component made from a dimer diol derived from a polymerized fatty acid having a main component (a conjugated fatty acid) is particularly preferred.

  The number average molecular weight of the repeating unit of the polyester component used in the present invention is preferably in the range of 800 to 3000, and more preferably in the range of 1000 to 2000. When the number average molecular weight is 800 or less, the solvent cracking resistance is poor, and conversely, when the number average molecular weight is 3000 or more, the compatibility with the polyamide-forming monomer is poor and a good block copolymer cannot be obtained.

Production Method As a method for producing the thermoplastic polyamide elastomer resin (B), any method may be used as long as a uniform and high molecular weight polymer can be obtained. For example, at least a part of the end groups obtained from the amidation reaction of the polyamide-forming monomer is first an amino group and / or
Alternatively, a polyamide oligomer whose reaction is stopped by a hydroxyl group is synthesized, and an ether ester and / or a polyester-forming component are blended therein, and heated under a reaction condition of 200 to 300 ° C. under reduced pressure, and an esterification reaction is performed using an esterification catalyst. To increase the degree of polymerization.

  The esterification catalyst used here is a known catalyst, for example, phosphoric acid-based catalysts such as phosphoric acid, metaphosphoric acid, polyphosphoric acid, titanium-based catalysts such as tetrabutyl orthotitanate and tetraisopropyl orthotitanate, dibutyltin oxide, Tin-based catalysts such as dibutyltin laurate and monobutylhydroxytin oxide, and zirconium-based catalysts such as tetrabutoxyzirconium, zirconium acetate, and zirconium octylate are used.

  As the thermoplastic polyamide elastomer resin (B), a commercially available product may be used. Specifically, TPAE-237CP-5A (polyether ester amide, amino group terminal type) manufactured by Fuji Kasei Kogyo Co., Ltd., TPAE- 617 (polyesteramide, hydroxyl-terminated type) and TPAE-617C (polyesteramide, amino-terminated type) can be used.

[Other ingredients]
Various additives can be blended in the ionomer resin composition of the present invention within a range not impairing the object of the present invention. Such additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, waxes, weathering stabilizers, pigments, dyes, lubricants, antiblocking agents, antistatic agents, antifungal agents, antibacterial agents , Flame retardants, flame retardant aids, foaming agents, foaming aids, inorganic fillers, fiber reinforcements and the like.

  In particular, in order to withstand long-term outdoor use, it is desirable to blend at least one selected from an antioxidant, a light stabilizer and an ultraviolet absorber. As an antioxidant, as a hindered phenol antioxidant represented by tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, a light stabilizer, As a hindered amine light stabilizer represented by bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, an ultraviolet absorber is represented by 2-hydroxy-4-n-octoxybenzophenone. Benzotriazole ultraviolet absorbers typified by benzophenone ultraviolet absorbers and 2- (2′-hydroxy-5′-methylphenyl) benzotriazole are preferably used. These effective addition amounts are each preferably 5 parts by weight or less, particularly preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight in total of the ionomer resin (A) and the thermoplastic polyamide elastomer (B).

[Ionomer resin composition]
The ionomer resin composition of the present invention contains an ionomer resin (A) and a thermoplastic polyamide elastomer (B). The blending ratio of the ionomer resin (A) and the thermoplastic polyamide elastomer (B) is 1 to 20 parts by weight, preferably 2 to 18 parts by weight, more preferably 5 to 5 parts by weight with respect to 100 parts by weight of the ionomer resin (A). An amount of 15 parts by weight. Thereby, the mechanical properties can be improved while maintaining the transparency of the resin composition. However, if the blending ratio exceeds the above range, the mechanical properties are impaired, which is not preferable.
The melt flow rate (based on JIS K7210-1999) of the ionomer resin composition of the present invention varies depending on the type and blending ratio of the ionomer resin to be used, but is usually 0.01 to 500 g / 10 min. It is preferably in the range of about 1 to 300 g / 10 minutes.

The ionomer resin composition of the present invention can be obtained by melt blending the above ionomer resin (A), the thermoplastic polyamide elastomer (B), and other additives as required, simultaneously or sequentially. In the case of melt blending, a kneading apparatus such as a single-screw or twin-screw extruder, a Banbury mixer, a roll, or a kneader may be used and melt-kneaded at a temperature of about 220 to 250 ° C.

[Molded body and method for producing the same]
The ionomer resin composition of the present invention is a suitable material that can be applied to publicly known molding methods, and the molded product obtained is not particularly limited, and examples thereof include molded products such as automobile parts and sheets. Among these, a transparent design member and an optical member that require transparency and mechanical strength are particularly suitable applications.

  The molding method of the molded body formed from the ionomer resin composition of the present invention includes injection molding, blow molding (injection stretch blow, extrusion stretch blow, direct blow), balloon method, inflation molding, coextrusion method, and calendar. Method, hot press method, solvent casting method, (drawing) extrusion molding, profile extrusion molding, thermoforming such as vacuum (pressure air) molding, melt spinning (monofilament, multifilament, spunbonding method, meltblown method, etc.), defibrating yarn And foam molding methods such as extrusion foaming and mold foaming, compression molding methods, etc., and any method can be used. Of these, injection molding or the like is preferably used.

  The thickness of the sheet formed from the ionomer resin composition of the present invention can be variously changed depending on the use, but generally speaking, it is desirable to be in the range of 1 to 500 μm, preferably 50 to 200 μm. Moreover, the said sheet | seat can be used as a laminated body by bonding or coextrusion using a conventionally well-known sheet | seat, the various base material used normally, and an adhesive agent or adhesive resin.

〔Example〕
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this. In addition, the physical-property evaluation method in an Example and a comparative example is as follows.
(1) Melt flow rate (MFR): Conforms to JIS K-7210 Load x temperature: 2,160 g x 190 ° C
(2) Optical characteristics (0.5mm thickness)
Total light transmittance: compliant with JIS K-7105 Haze: compliant with JIS K-7105 (3) Hardness (Shore D): compliant with JIS K-7215 (4) Flexural rigidity (MPa): compliant with JIS K-7106 Test piece: 20 × 100 × 3 (mm)
(5) Tensile properties:
The measurement was performed according to JIS K6760.

Test piece: JIS K6301 thermoplastic polyamide elastomer used in the No. 2 dumbbell 2mm thickness (B) of the present invention, (b2) obtained by copolymerization of Po Li amide oligomer and the polyester component, at least a portion of the end groups amino It is a thermoplastic polyamide elastomer (B) made of a polyesteramide block copolymer that has been stopped to have a group and / or a hydroxyl group . In the present embodiment, a reportage Li ester amide block copolymer having a amino group or hydroxyl group at the terminus.

[ Reference Example 1]
90% by mass of zinc ionomer (degree of neutralization 59%; MFR 0.9 g / 10 min) of an ethylene / methacrylic acid copolymer (methacrylic acid content 15% by weight; MFR 60 g / 10 min), and a polyether ester amide A block copolymer (amino group terminal type) and 10% by mass were melt mixed at 220 ° C. with a single screw extruder to prepare a resin composition. In addition, as a polyether ester amide block copolymer (amino group terminal type), trade name: TPAE-237CP-5A (Fuji Kasei Kogyo Co., Ltd .; melt viscosity 140 Pa · S (250 ° C.); melting temperature = 157 / 177 ° C .; flexural modulus = 92 MPa; acid value = 1.8; amine value = 4.2; surface resistivity = 1.37 × 10 ⁹ (Ω); saturated water absorption = 42%).
Here, the acid value refers to the terminal carboxyl group concentration, and 1 mg of a sample is dissolved in 50 g of benzyl alcohol, and the number of mg of KOH when titrated with a 1/10 N KOH methanol solution using a phenolphthalein indicator. expressed. The amine value refers to the terminal amino group concentration, and 1 mg of a sample is dissolved in 50 g of a phenol / methanol mixed solution, and the number of mg of hydrochloric acid when titrated with 1/10 N hydrochloric acid methanol solution using a bromophenol blue indicator. expressed. Hydroxyl value refers to the concentration of terminal hydroxyl groups, and 1 to 6 g of sample is dissolved in an acetylating reagent (1 g of acetic anhydride dissolved in 25 g of pyridine) and then titrated with a 1/2 N KOH isopropanol solution. The number of mg of KOH was shown.

[Example 2]
A resin composition was prepared in the same manner as in Reference Example 1, except that the polyester ester amide block copolymer (amino group terminal type) was replaced with the polyester amide block copolymer (hydroxyl terminal type). In addition, as a polyesteramide block copolymer (hydroxyl terminal type) in Example 2, trade name: TPAE-617 (Fuji Kasei Kogyo Co., Ltd .; melt viscosity 43.7 Pa · S (230 ° C.); MFR (190 ° C.) × 21.18N) = 17 g / 10 min; melting temperature = no peak; flexural modulus = 870 MPa; acid value = 0.4; hydroxyl value = 16).

[Example 3]
A resin composition was prepared in the same manner as in Reference Example 1, except that the polyester ester amide block copolymer (amino group terminal type) was replaced with a polyesteramide block copolymer (amino group terminal type). In addition, as a polyesteramide block copolymer (amino group terminal type), trade name: TPAE-617C (manufactured by Fuji Kasei Kogyo; MFR (190 ° C. × 21.18N) = 17.9 g / 10 min; flexural modulus = 700 MPa; acid value = 0.6; amine value = 8.2; melting temperature = no peak).

[Comparative Example 1]
Physical property values were measured using only a zinc ionomer (degree of neutralization 59%; MFR 0.9 g / 10 min) of an ethylene / methacrylic acid copolymer (methacrylic acid content 15% by weight; MFR 60 g / 10 min). .

[Comparative Example 2]
Reference Example 1 except that the polyether ester amide block copolymer (amino group terminal type) was changed to a copolymer of dimer acid and short chain dibasic acid (type having no amino group or hydroxyl group at the terminal) In the same manner as above, a resin composition was prepared. As the polyamide, PA-30 (manufactured by Fuji Kasei Kogyo; MFR (230 ° C. × 21.18 N) = 11 g / 10 min; flexural modulus = 950 MPa; acid value = 0.9; melting temperature = 200 ° C.) Was used.

[Comparative Example 3]
A resin composition was prepared in the same manner as in Reference Example 1 except that the polyester ester amide block copolymer (amino group terminal type) was changed to a polyesteramide block copolymer (type having no amino group or hydroxyl group at the terminal). Prepared. The polyesteramide block copolymer includes TPAE-63 (Fuji Kasei Kogyo Co., Ltd .; MFR (190 ° C. × 21.18N) = 5.4 g / 10 min; melting temperature = 172 ° C .; flexural modulus = 250 MPa. Acid value = 1.0) was used.

[Comparative Example 4]
Resin composition in the same manner as in Reference Example 1 except that the polyether ester amide block copolymer (amino group terminal type) was changed to a polyether ester amide block copolymer (type having no amino group or hydroxyl group at the terminal). A product was prepared. As the polyetheresteramide block copolymer, TPAE-H151 (Fuji Kasei Kogyo Co., Ltd .; MFR (190 ° C. × 21.18 N) = 13.1 g / 10 min; melting temperature = 152/173 ° C .; flexural elasticity Rate = 73 MPa; acid value = 0.6; surface resistivity (Ω) = 5.32 × 10 ⁷ ; saturated water absorption = 65%).

  The ionomer resin composition of the present invention is excellent in transparency and mechanical strength, and can suitably form molded articles such as automobile parts and sheets.

Claims (3)

100 parts by weight of ionomer resin (A) ,
(B2) Po Li amide obtained by copolymerization of the oligomer and the polyester component, the end groups of the thermoplastic polyamide comprises a reaction stop polyester amide block copolymer to have at least part of the amino group and / or hydroxyl An ionomer resin composition comprising 1 to 20 parts by weight of an elastomer (B).   The ionomer resin composition according to claim 1, wherein the ionomer resin (A) is an ionomer of an ethylene / unsaturated carboxylic acid copolymer.   The molded object formed from the ionomer resin composition of Claim 1 or 2.