JPH1129672A - Ionomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition for materials for golf balls, etc., capable of readily molding and processing without emitting smoke in thermoforming at high temperature and excellent in physical properties such as rigidity by using a small amount of specific organic carboxylic acid compound. SOLUTION: This ionomer composition is preferably obtained by compounding (A) an ethylene-unsaturated carboxylic acid copolymer having 2-30 wt.% unsaturated carboxylic acid content and 0.1-1,500 g/10 min melt flow rate (at 190 deg.C under 2160 g load) or a metal ionomer of the ethylene-unsaturated carboxylic acid copolymer with (B) an amine compound having two primary or secondary amino groups and (C) an organic carboxylic acid having carboxyl group with 2-7 acid dissociation equilibrium constant (pKa), e.g. adipic acid in an amount capable of preventing fuming in melting. Furthermore, the component B and component C are each preferably compounded in an amount satisfying the equations I, II and III (X is a molar ratio of amino group of the component B to total carboxyl group of the component A; Y is a molar ratio of carboxyl group of the component C to amino group of the component B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ionomer composition which does not emit smoke during thermoforming, is excellent in moldability, and has excellent physical properties such as resilience, rigidity, hardness, bending resistance and tensile strength.

[0002]

2. Description of the Related Art Ionomers are used for various molding materials, such as golf ball materials, because of their excellent mechanical properties and excellent durability. Further improvement is desired.

As a means for improving the hardness, rigidity and rebound resilience of ionomers, it is known that the addition of certain diamines is effective. Among them, aromatic or alicyclic compounds having a bisaminoalkyl group are known. What was blended,
Japanese Patent Application Laid-Open No. 61-9-9 shows that stiffness, hardness, etc. are improved and that smoke and coloring during melt molding are small and practical.
No. 403 and Japanese Patent Application Laid-Open No. 61-281145. Japanese Patent Application Laid-Open No. 61-501455 also proposes a modification of an ionomer with a similar amine, although the purpose is different.

Further, an ethylene / unsaturated carboxylic acid copolymer or a polyvalent metal ionomer of an ethylene / unsaturated carboxylic acid copolymer, which contains an organic amine compound having two or more primary or secondary amino groups, Because of its excellent resilience, rigidity, bending resistance, low-temperature adhesiveness, and injection moldability, and it can be recycled, it has been previously proposed to be used as a material for golf balls, shoe counters, packaging materials, etc. ( For example, Japanese Patent Application No. 8-33704, filed by the present applicant,
Japanese Patent Application Nos. 8-305049 and 8-112826.

[0005] Further, a method using a high molecular weight amine compound for modifying an ionomer or the like has been proposed (for example, Japanese Patent Application No. 8-112826).

[0006]

However, ionomer compositions to which these organic amine compounds have been added tend to emit smoke during thermoforming, though to varying degrees, and are particularly required for injection molding applications. At a melting temperature of 200 ° C. or higher, the problem of smoke generation has not been solved.

When a high-molecular-weight amine compound or polyamine compound is used, smoke generation is suppressed due to an increase in the boiling point of the amine compound, but the heat fluidity of the resin is remarkably reduced, and molding processability is lost. Tend to be

Under the circumstances described above, at present, there is no other solution to this problem than molding at a low temperature, and it cannot be used in applications requiring high-temperature molding such as injection molding.

Therefore, the present inventors have found that while maintaining resilience, rigidity, bending resistance, low-temperature adhesion, injection moldability, weather resistance, and recyclability, they do not emit smoke at the time of thermoforming at a high temperature. Various studies were made on an organic amine-modified ionomer composition that was easy to process. As a result, the purpose can be achieved by using a small amount of a specific organic carboxylic acid compound,
The present inventors have found that a thermoplastic ionomer composition which can be easily thermoformed has been obtained, and have reached the present invention.

[0010]

According to the present invention, (A)
Unsaturated carboxylic acid content is 2 to 30% by weight, melt flow rate (190 ° C., 2160 g load) is 0.1 to 15
(B) a primary or secondary amino group is added to the ethylene / unsaturated carboxylic acid copolymer or the metal ionomer of the ethylenically unsaturated carboxylic acid copolymer at a rate of 00 g / 10 min.
And the (C) acid dissociation equilibrium constant (pK
An ionomer composition is provided, wherein a) is prepared by mixing an organic carboxylic acid having 2 to 7 carboxyl groups in an amount capable of preventing fumes upon melting. In the present invention, the amine compound (B) and the organic carboxylic acid (C) are converted into the following formula: 0.01 ≦ X ≦ 1 {(1) 0.001 ≦ Y ≦ 0.1} (2) and 0.034X ² ≦ Y ≦ 0.034X ² +0.051 (3) In the formula, X represents the molar ratio of the amino group of the component (B) to the total carboxyl groups of the component (A), and Y represents the amino group of the component (B). , Which represents the molar ratio of the carboxyl group of the component (C) to the carboxyl group. The organic carboxylic acid is an aliphatic or alicyclic carboxylic acid, and the organic carboxylic acid has 3 to 20 carbon atoms.
Is preferred. According to the present invention, there is further provided an ionomer molded article comprising the above ionomer resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION

[Action] In the present invention, the compound (B) having two or more primary or secondary amino groups in the ethylene / unsaturated carboxylic acid copolymer or the metal ionomer (A) of the ethylenically unsaturated carboxylic acid copolymer And specific acid dissociation equilibrium constant (pKa)
And an organic carboxylic acid having a characteristic of being combined in an amount such that fumes at the time of melting are prevented,
As a result, while maintaining the inherent resilience, rigidity, bending resistance, low-temperature adhesion, injection moldability, weatherability, and recyclability of the organic amine-modified ionomer composition, smoke is generated during high-temperature thermoforming. And the generation of amine odor
Formability can be improved.

The present invention provides a finding that an organic carboxylic acid having a pKa of 2 to 7, especially an aliphatic or alicyclic carboxylic acid, is useful for preventing generation of smoke and amine odor during melting of an organic amine-modified ionomer composition. It is based on.

It is considered that the smoke emission in the organic amine-modified ionomer composition is caused by a part of the amines added to the ionomer or the like being taken into the polyethylene crystal part of the ionomer or the like. It is presumed that it acts on some amines to prevent fuming. Therefore, unless the carboxylic acid is easily incorporated into the polyethylene crystal part, the amine contributing to the improvement of the physical properties is consumed, and the physical properties are reduced. This tendency is also observed when the amount of the carboxylic acid is too large.

In the present invention, the compounding amount of the organic carboxylic acid (C) depends on the compounding amount of the organic amine compound (B).
The amount is preferably in the range defined by the above formulas (1), (2) and (3). FIG. 1 is a graph in which the blending amount of amines (B) is plotted on the horizontal axis and the blending amount of organic carboxylic acid is plotted on the vertical axis in Examples and Comparative Examples described later. Indicates that there is no generation and physical properties are good, and the mark “x” indicates that there is generation of smoke or amine odor or that the physical properties are remarkably deteriorated. According to these results, in the region below the curve A (Y = 0.034X ² ), the generation of smoke and amine odor was remarkable, while the region above the curve B (Y = 0.034X ² +0.051). In the region surrounded by these curves, the physical properties are remarkably reduced, whereas in the region surrounded by these curves, no smoke or amine odor is generated, and the physical properties are maintained at an excellent level.

[Component (A)] The component (A) used in the present invention is an ethylene / unsaturated carboxylic acid copolymer or a metal ionomer of an ethylene / unsaturated carboxylic acid copolymer.

The ethylenically unsaturated carboxylic acid copolymer used as the component (A) has an unsaturated carboxylic acid content of 2%.
-30% by weight, melt flow rate (190 ° C., 216
(E.g., 0 g load) of 0.1 to 1500 g / 10 min. In addition, this ethylene unsaturated carboxylic acid copolymer, not only a narrowly defined copolymer consisting of only ethylene and unsaturated carboxylic acid, but also optionally a multi-component copolymer in which other copolymerization components are copolymerized Good. Also, a mixture of different or plural ethylene / unsaturated carboxylic acid copolymers can be used.

As unsaturated carboxylic acids, acrylic acid,
Examples include methacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, maleic acid monoester, maleic anhydride, itaconic anhydride and the like. Particularly, use of acrylic acid or methacrylic acid is preferred.

Further, optional other copolymer components include:
Unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, isobutyl methacrylate, dimethyl maleate and diethyl maleate, vinyl acetate, vinyl propionate And vinyl monoxide, carbon monoxide, and the like.

In the ethylene / unsaturated carboxylic acid copolymer, the content of unsaturated carboxylic acid is 2 to 30% by weight, preferably 5 to 25% by weight. May be copolymerized in a proportion of generally 40% by weight or less, preferably 30% by weight or less. If an ethylene acid copolymer having too high an acid content is used, it becomes very brittle and cannot be used. On the other hand, if the other copolymerization component is excessively copolymerized, it is too soft to obtain sufficient rebound resilience.

Such an ethylene / unsaturated carboxylic acid copolymer can be preferably obtained by high-pressure radical copolymerization. The ethylene / unsaturated carboxylic acid copolymer can be obtained by hydrolysis of the ethylene / unsaturated carboxylic acid ester copolymer.

On the other hand, the metal ionomer of the ethylene / unsaturated carboxylic acid copolymer can be obtained by ionizing the above-mentioned ethylene / unsaturated carboxylic acid copolymer by a conventional method.

In the metal ionomer of the ethylene / unsaturated carboxylic acid copolymer, the metal ion may be a monovalent ion such as lithium, sodium, potassium and cesium; a divalent ion such as zinc, magnesium and calcium;
Trivalent ions such as aluminum can be exemplified, and among these, divalent ions such as magnesium and zinc are particularly preferable. Further, two or more of the metal ions shown here can be used simultaneously.

The degree of neutralization of these carboxyl groups in the ionomer is preferably 20 mol% or more, and most preferably 25 to 80 mol%, in consideration of resilience and impact resistance. In consideration of the hardness and resilience characteristic of the ionomer, the degree of neutralization is most preferably 40 to 80 mol%.

In view of various physical properties such as moldability, the metal ionomer of the ethylene / unsaturated carboxylic acid copolymer obtained by ionization is, for example,
The melt flow rate at 190 ° C. and a load of 2160 g is about 0.1 to 1000 g / 10 min, preferably 0.5
It is preferable to use one of about 300 g / 10 min. When an ionomer having a higher degree of neutralization is used, the fluidity at the time of melting is significantly reduced, and the moldability tends to deteriorate.

[Component (B)] As the component (B) in the present invention, a compound containing two or more primary or secondary amino groups is used. Those in which the primary or secondary amino group is an aminoalkyl group or an aminocycloalkyl group are preferred. As the component (B), an aliphatic, alicyclic or aromatic compound can be used, but an alicyclic or aromatic compound is preferable in view of the composition and the physical properties of the molded product, and a condensed ring is particularly preferable. Those having two or three are most preferred.

More specifically, examples of the amino compound include aliphatic amines such as hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6,9,12-tetraoxa-tetradecane-1,14 diamine, and the like. , 3-bisaminomethylcyclohexane,
1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, isophoronediamine, 2,5 (or 2,6) -bis (aminomethyl) bicyclo [2,2,1] Heptane,
2,6 (or 2,7) -bis (aminomethyl) bicyclo [3,2,1] octane, 2,5 (or 2,6) -bis (aminomethyl) -7-dimethylbicyclo [2,2
1] alicyclic amines such as heptane, 2,6-bis (aminomethyl) adamantane, m-xylylenediamine;
p-phenylenediamine, bis (4-aminophenyl)
Such as methane, 1,4 (or 2,6 or 2,7) -bis (aminomethyl) naphthalene, aromatic diamine such as a reaction product of m-xylenediamine and epichlorohydrin, piperazine, aminoethylpiperazine, bisaminopropylpiperazine Heterocyclic amines can be exemplified. These amino compounds (B) can be used in combination of two or more.

The proportion of component (B) used is based on the carboxyl group in the ethylene / unsaturated carboxylic acid copolymer or the metal ionomer (A) of the ethylenically unsaturated carboxylic acid, and the primary or secondary amino group is 0.1 to 0.1%. 01 to 1 equivalent,
Preferably, it is used in a ratio of 0.1 to 0.8 equivalent. Even if the compounding ratio of (B) is used in an amount exceeding 1 equivalent to the carboxyl group of component (A), no improvement in physical properties can be expected, and the quality may be deteriorated due to bleed-out from the molded product. Absent.

[Component (C)] The component (C) in the present invention is an organic carboxylic acid having a carboxyl group having an acid equilibrium constant (pKa) of 2 to 7, preferably 3 to 6. In the present invention, when the organic carboxylic acid has a plurality of pKas, it refers to the minimum pKa.

More specifically, formic acid (pKa; 3.5)
5), acetic acid (pKa; 4.56), propionic acid (pK
a; 4.67), butanoic acid (pKa; 4.63), pentenoic acid (pKa; 4.68), hexanoic acid (pKa;
4.63), linear aliphatic monocarboxylic acids such as heptanoic acid (pKa; 4.66), and succinic acid (pKa ₁ ; 4.0).
0, pKa ₂ ; 5.24), glutanic acid (pKa ₁ ;
4.13, pKa ₂ ; 5.03), adipic acid (pKa
₁ ; 4.26, pKa ₂ ; 5.03), pimelic acid (p
_{Ka 1; 4.31, pKa 2;} 5.08), suberic acid _{(pKa 1; 4.35, pKa 2} ; 5.10), azelaic acid _{(pKa 1; 4.39, pKa 2} ; 5.12) ,
Malic acid (pKa ₁ ; 3.24, pKa ₂ ; 4.7)
1), terephthalic acid (pKa ₁ ; 3.54, pKa ₂ ;
4.46), aliphatic and aromatic dicarboxylic acids, crotonic acid (pKa; 4.69), acrylic acid (pKa; 4.46).
26), unsaturated carboxylic acids such as methacrylic acid (pKa; 4.66), anisic acid (pKa; 4.09), and m-aminobenzoic acid (pKa ₁ ; 3.12, pKa ₂ ; 4.7).
4), m-, p- chlorobenzoic acid (pKa _m; 3.8
2, pKa _p; 3.99), hydroxybenzoic acid (pK
_{a 1; 4.08, pKa 2;} 9.96) aromatic carboxy compounds including benzoic acids such as citric acid (pKa _1;
2.87, pKa ₂ ; 4.35, pKa ₃ ; 5.69)
And polycarboxylic acids and derivatives thereof. In addition, rosins can also be used. Among them, aliphatic or alicyclic carboxylic acids are preferable, and those having 3 to 20 carbon atoms, particularly about 4 to 10 carbon atoms, are preferable because they have a smoke-preventing effect when used in a small amount.

When an organic carboxylic acid having a pKa smaller than the range specified in the present invention is used, it reacts violently with the diamine,
Not only do salts form and the dispersion in the resin becomes insufficient, but also the physical properties of the resin itself are significantly reduced. On the other hand, if the pKa is larger than the above range, the smoke suppressing effect is significantly reduced. Among these organic carboxylic acids, adipic acid is most preferable in consideration of performance, workability and cost.

The appropriate amount of the component (C) varies slightly depending on the type of the component (B), but the carboxyl group of the component (C) has a molar ratio of (C) to the amino group of the component (B). Carboxyl group of component / amino group of component (B) =
0.001 to 1, preferably 0.001 to 0.1, and is preferably blended so as to satisfy the above formula (3). If the amount of component (C) is less than the specified amount, sufficient smoke control performance cannot be obtained. On the other hand, when the amount of the component (C) is more than the specified amount, the characteristic physical properties of the ionomer such as resilience and rigidity are significantly reduced.

[Composition] The ionomer resin of the present invention comprises:
It is obtained by heating and mixing the components (A), (B) and (C). This heating and mixing is performed under a temperature condition of 150 to 280 ° C. using a single screw extruder, a twin screw extruder, or a usual melt mixing or processing apparatus for thermoplastic resin such as a Banbury mixer or a kneader.

The order of mixing the three components is not particularly limited.
After blending the component and the component (B), the component (C) may be blended, or the component (B) may be blended after the component (C) is blended with the component (A). Further, when the component (C) is not a liquid, the components (A) and (C) can be dry-blended in advance, and then the component (B) can be blended.
In any case, the present invention is not limited to such a manufacturing method.

The ionomer composition of the present invention contains the above 3
In addition to the components, various additives may be blended as long as the object of the present invention is not impaired. As additives, various colorants,
Examples thereof include an antioxidant, an antistatic agent, a dispersant, and an inorganic filler.

The ionomer composition of the present invention can be obtained by injection molding,
Various molded articles can be produced by molding methods such as blow molding, sheet molding, and pipe molding, and are particularly useful as skin materials for golf balls.

[0036]

Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to only these examples. Ethylene / unsaturated carboxylic acid (hereinafter referred to as an acid copolymer) used in the following Examples and Comparative Examples, or a metal ionomer [(A) component], an amine compound [(B) component], and an organic carboxylic acid [( C) component].

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

The physical properties in the examples and comparative examples were measured by the following methods.

Method of measuring physical properties Melt flow rate (MFR): JIS K-676
0, temperature 190 ° C, load 2160g ・ Hardness (Shore D): JIS K-7215 compliant 3mm thick sheet hot-pressed at 160 ° C (190 ° C when using an ionomer) at 23 ° C, 50% relative humidity After adjustment for 14 days in an atmosphere, the sheet was punched out to obtain a test specimen, which was then subjected to a test. -Rebound resilience: JIS K-6301 compliant 160 ° C (190 ° C when an ionomer is used) Hot-press molded at a thickness of 13.0mm and a diameter of 29.0mm
The test was performed by adjusting the temperature of the sample at 23 ° C. and 50% relative humidity for 14 days. -Flexural rigidity: According to JIS K7106, a 3 mm thick sheet hot-pressed at 160 ° C (190 ° C when an ionomer is used) is adjusted in an atmosphere of 23 ° C and 50% relative humidity for 14 days, and this sheet is punched out. The test was performed as a test specimen. -Tensile test: A 2 mm thick sheet hot-pressed at 160 ° C (190 ° C when using an ionomer) in accordance with JIS K6760 No. 2 was adjusted for 14 days in an atmosphere of 23 ° C and 50% relative humidity, and this sheet was punched out. The test pieces were used as test specimens. The evaluation result was elongation / stress at break (% / MPa).・ Smoke suppression evaluation Evaluation was performed using a 30 mmφ single screw vent extruder manufactured by Thermoplastics Co., Ltd. at 180 ° C. (230 ° C. when an ionomer was used), and the screw rotation speed was 40 min.
Evaluation of smoke and amine odor from the vent port, the die port, and the strand surface during thermoforming with -1. Evaluation 1: When using a diamine-modified acid copolymer ○: When extruded under the condition of 180 ° C.,
No smoke is emitted from any of the vent, die, or strand surface. ×: When extrusion molding was performed under the condition of 180 ° C.,
Smoke is generated from at least a part of the vent port, the die port, and the strand surface. Evaluation 2: In the case of using a diamine-modified ionomer ○: When extruded at 230 ° C.,
No smoke is emitted from any of the vent, die, or strand surface. ×: When extrusion molding was performed at 230 ° C.,
Smoke is generated from at least a part of the vent port, the die port, and the strand surface. -Evaluation of amine odor suppression Evaluation 1: When a diamine-modified acid copolymer was used. ：: When extrusion molding was performed at 180 ° C,
No amine odor is observed from any of the vent port, die port and strand surface. ×: When extrusion molding was performed under the condition of 180 ° C.,
An amine odor is generated from at least a part of the vent port, the die port, and the strand surface. Evaluation 2: In the case of using a diamine-modified ionomer ○: When extruded at 230 ° C.,
No amine odor is observed from any of the vent port, die port and strand surface. ×: When extrusion molding was performed at 230 ° C.,
An amine odor is generated from at least a part of the vent port, the die port, and the strand surface. -Appearance ：: No cloudy bleed-out was observed. X: Cloudy bleed-out is observed.

EXAMPLES / COMPARATIVE EXAMPLES The compositions having the formulations shown in the table were prepared using a 30 mmφ single screw vent extruder manufactured by Thermoplastics Co., Ltd. at 180 ° C. (230 ° C. when an ionomer was used) and at a screw rotation speed of 40 min. 1 and melt blended. The compounding method of the mixture was to prepare a diamine-modified acid copolymer and a diamine-modified ionomer in advance, then dry-blend the organic carboxylic acid, and then melt-blended under the above conditions. The physical properties of the obtained heat-mixed composition were evaluated and summarized.

Comparative Example 1 In Comparative Example 1, an amount of the amine compound 1 having an amino group equivalent to 80 mol% with respect to the carboxyl group of the acid copolymer 1 was added to the acid copolymer 1. The composition of Comparative Example 1 has high resilience, rigidity, hardness, and tensile strength. However, as shown in Table 6, not only extrusion molding at 180 ° C., but also significant fuming and amine odor are generated at the stage of thermoforming such as injection molding, and the molding processability is clearly inferior.

Example 1 In Example 1, an acid copolymer 1 was added to the composition described in Comparative Example 1.
This is a composition in which a low-molecular-weight carboxylic acid 1 having an amount of a carboxyl group equivalent to 4 mol% with respect to the carboxyl group is mixed. Table 6 shows the evaluation results. The composition of Example 1 comprises
It has the same resilience, rigidity, hardness, and tensile strength as Comparative Example 1, and also maintains good moldability. further,
No change in the resin properties such as the melting points of MFR and PE was observed. That is, the composition shown in Example 1 had no smoke or amine odor even at the time of processing at 180 ° C., and had good thermal stability.

Example 2 Example 2 is a composition obtained by mixing low-molecular carboxylic acid 2 in place of low-molecular carboxylic acid 1 in Example 1.
Table 6 shows the evaluation results. The composition of Example 2 is the same as Example 1
It has the same resilience, rigidity, hardness, and tensile strength as, and also maintains good moldability.

Comparative Examples 2 to 4 In Example 1, low molecular carboxylic acid 1 was used in the amounts shown in Table 5. Table 6 shows the evaluation results. Although the compositions shown in Comparative Examples 2 and 3 have the same smoke suppressing and amine odor suppressing properties as the composition shown in Example 1, the resin becomes cloudy due to the excessively present low-molecular carboxylic acid 1, resulting in transparency. Is lost. Further, the resilience of the compositions shown in Comparative Examples 2 and 3,
The rigidity, hardness, and tensile strength are significantly lower than those of the composition shown in Comparative Example 1, and the desired performance cannot be obtained. The composition shown in Comparative Example 4 has the same resilience, rigidity, hardness, tensile strength and resin properties as the composition shown in Comparative Example 1, but the amount of the low-molecular carboxylic acid 1 added is small, and Fuming and amine odor.

[0048]

[Table 5]

[0049]

[Table 6]

Comparative Example 5 In Comparative Example 5, the amount of the amine compound 1 having an amino group equivalent to 39 mol% with respect to the carboxyl group of methacrylic acid was added to the ionomer 1. The evaluation results are shown in Table 8, and the composition shown in Comparative Example 5 had high resilience,
It has rigidity, hardness and tensile strength. However, of course, extrusion at 230 ° C., which is a general thermoforming condition,
At the stage of thermoforming such as injection molding, remarkable fuming and amine odor are generated, and molding processability is clearly inferior.

Examples 3 to 5 Examples 3 to 5 are compositions obtained by blending the composition described in Comparative Example 5 with the amount of low molecular carboxylic acid 1 shown in Table 7. Table 8 shows the evaluation results. The compositions of Examples 3 to 5 have the same resilience, stiffness, hardness, and tensile strength as Comparative Example 5, and also maintain good moldability. In addition, MFR
Also, no change in the physical properties of the resin such as the melting point of PE was observed. That is, the composition shown in Examples 3 to 5 was 230 ° C.
No fuming or amine odor was observed even during processing with, and it had good thermal stability.

Example 6 In Examples 3 to 5, low-molecular carboxylic acid 2 was used in place of low-molecular carboxylic acid 1. Table 8 shows the evaluation results. The composition of Example 6 has resilience, rigidity, hardness and tensile strength equivalent to those of the compositions of Examples 3 to 5, and also maintains good moldability.

Comparative Example 6 Comparative Example 6 is a composition obtained by blending the composition described in Comparative Example 5 with the amount of adipic acid shown in Table 7. Table 8 shows the results. The composition of Comparative Example 6 has the same smoke and amine odor suppressing ability as those of Examples 3 to 5, but the resilience, rigidity, hardness, and tensile strength are significantly lower than those of the composition of Comparative Example 5. However, the desired performance cannot be obtained. Further, the resin properties such as the melting points of MFR and PE also change greatly.

[0054]

[Table 7]

[0055]

[Table 8]

Comparative Examples 7 and 8 In Comparative Examples 7 and 8, instead of the amine compound 1 shown in Comparative Example 5, amine compounds 2 and 3 in the amounts shown in Table 9 were blended, respectively. Table 10 shows the evaluation results.
As shown, the compositions of Comparative Examples 7 and 8 have high resilience, rigidity, hardness and tensile strength. However, not only extrusion molding at 230 ° C., which is a general thermoforming condition, but also significant fuming and amine odor are generated at the stage of thermoforming such as injection molding, and the molding processability is clearly poor.

Examples 7 and 8 Examples 7 and 8 show that the compositions described in Comparative Examples 7 and 8
It is a composition containing the low-molecular carboxylic acid 1 in the amounts shown in Table 9. Table 10 shows the evaluation results. The compositions described in Examples 7 and 8 have the same resilience, rigidity, hardness, and tensile strength as the compositions described in Comparative Examples 7 and 8, and maintain good moldability. That is, the compositions shown in Examples 7 and 8 did not emit smoke or amine odor even when processed at 230 ° C., and had good thermal stability.

[0058]

[Table 9]

[0059]

[Table 10]

[0060]

According to the present invention, the resilience and rigidity of an ethylene / unsaturated carboxylic acid copolymer modified with an amine compound or a polyvalent metal ionomer of an ethylenically unsaturated carboxylic acid copolymer are obtained. It is possible to provide an organic amine-modified ionomer composition which is easy to form without heat-forming smoke while maintaining characteristics such as adhesiveness, low-temperature adhesion, injection moldability, weather resistance, and recyclability.

[Brief description of the drawings]

FIG. 1 is a graph in which the amount of amines is plotted on the horizontal axis and the amount of organic carboxylic acid is plotted on the vertical axis in Examples and Comparative Examples.

Claims (5)

[Claims] (1) The content of (A) the unsaturated carboxylic acid is 2 to 3
0% by weight, melt flow rate (190 ° C., 2160 g
Ethylene) having a load of 0.1 to 1500 g / 10 min.
(B) an amine compound having two or more primary or secondary amino groups and (C) an acid dissociation equilibrium constant with respect to an unsaturated carboxylic acid copolymer or a metal ionomer of an ethylenically unsaturated carboxylic acid copolymer. An ionomer composition comprising an organic carboxylic acid having a carboxyl group having a pKa of 2 to 7 in an amount capable of preventing smoke from being generated during melting. 2. An amine compound (B) and an organic carboxylic acid (C) are synthesized by the following formula: 0.01 ≦ X ≦ 1 0.001 ≦ Y ≦ 0.1 and 0.034X ² ≦ Y ≦ 0.034X ² +0 In the formula, X represents the molar ratio of the amino group of the component (B) to the total carboxyl groups of the component (A), and Y represents the molar ratio of the carboxyl group of the component (C) to the amino group of the component (B). The ionomer composition according to claim 1, wherein the ionomer composition is blended in an amount satisfying the following. 3. The ionomer composition according to claim 1, wherein the organic carboxylic acid is an aliphatic or alicyclic carboxylic acid. 4. The ionomer composition according to claim 1, wherein the organic carboxylic acid is an organic carboxylic acid having 3 to 20 carbon atoms. 5. An ionomer molded article comprising the thermoplastic resin composition according to claim 1.