JPH02208340A - Resin composition of improved melt moldability - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is excellent in long run properties and can give a good-quality molding stably for a long time even when melt- molded at a temperature higher than the conventional one by mixing an ethylene/vinyl acetate copolymer saponificate with a fluororesin and a specified polyamide resin. CONSTITUTION:This resin composition comprises an ethylene/vinyl acetate copolymer saponificate (1), a fluororesin (2) and a polyamide resin (3) which satisfies the relationship B/(A+B)X100>=5 [wherein A is the number of the terminal carboxyl groups (-COOH), and B is the number of the terminal substituted amide groups (-CONRR') [wherein R is a 1-22C hydrocarbon group; and R' is a hydrogen atom or a 1-22C hydrocarbon group]]. The mixing ratio among the components is such that (1)/(3) is about 98/2-2/98 by weight, and (2) is about 10ppm-3% based on [(1)+(3)].

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a molding resin composition containing a saponified ethylene-vinyl acetate copolymer and a polyamide resin as main ingredients.
Prior Art] A composition of a saponified ethylene-vinyl acetate copolymer and a polyamide has oxygen barrier properties and Mi+ resistance based on the saponified product.
The melt-molded products are useful for food packaging films, sheets, and containers because they have useful properties such as anti-static properties, solvent resistance, antistatic properties, and aroma retention properties, as well as impact resistance based on polyamide. It is used for a variety of purposes.

However, when such compositions are melt-molded continuously over a long period of time, gels may be generated in the melt, and resin residue called discoloration may accumulate on a part of the extruder screw, discharge part, etc. This may damage the surface smoothness and appearance of the molded product, or in severe cases, the screen (wire mesh) or nozzle hole may become clogged, so the molding is temporarily stopped and the extruder is disassembled.
This tends to lead to practical problems such as poor long-run performance, which is forced to remove deposits, makes it practically impossible to continue molding for a long time, and limits the efficiency of molding work. be.

As a measure against this, (i) a special polyamide is added to the saponified ethylene-vinyl acetate copolymer, i.e. (iii)
The number (A) of the terminal group (-COOH) and the terminal substituted amide group (-CONRR') [However, R is a carbon number of 1 to
22 hydrocarbon group, Ro is a hydrogen atom or has 1 to 22 carbon atoms
It has been proposed to blend a polyamide resin which has a ratio of (B) to the number (B) of 100% hydrocarbon groups. It can be implemented.

[Problems to be Solved by the Invention] However, when the above composition is melt-molded at a relatively low temperature, it can be said that the long-run properties are sufficient, but as the molding temperature increases, the desired long-run properties are not necessarily obtained. It became clear that there was no.

It is necessary to melt and mold the composition of (i) and (iii) above at a high temperature because the melting point of the composition of (i) and (iii) is higher than that of the composition of (i) and (iii), such as nylon, polyester, polycarbonate, etc. This is the case, for example, when a laminate is manufactured by a coextrusion method from a resin and a composition having a high carbon content. In other words, in order to maintain a high level of adhesion between the layers of the laminate, it is essential that the respective extrudates extruded from the die do not have a large temperature difference, so the melting temperature of the high melting point resin Therefore, it is necessary to keep the molding temperature of the composition as close as possible.

[Means for Solving the Problems] As a result of extensive research, the present inventors have found that (i) saponified ethylene-vinyl acetate copolymer (i1)
fluorine-containing resin and (iii) the number (A) of terminal carboxyl groups (-coOH) and terminal substituted amide groups (-CONRR') [however,
R is a hydrocarbon group having 1 to 22 carbon atoms, Ro is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms] and a polyamide resin satisfying the following ratio: Even if melt molding is continued at a higher temperature than in the case of
The present invention was completed by discovering that molded products of good quality can be produced stably over a long period of time.

(i) The saponified ethylene-vinyl acetate copolymer used in the present invention has an ethylene content of 20 to 80 mol%, preferably 25 to 60 mol%, and a degree of saponification of the vinyl acetate component of 9.
0 mol % or more, preferably 95 mol % or more of radish is usually used. If the ethylene content is less than 20 mol %, the oxygen barrier properties at high humidity will decrease, while if it is more than 80 mol %, physical properties such as oxygen barrier properties and printability will deteriorate. Furthermore, if the degree of saponification is less than 90 mol%, oxygen barrier properties and moisture resistance will decrease.

Among these saponified products, the intrinsic viscosity (measured at 30°C as a 5% i water-containing phenol solution) is 0, 7~], 5
d(!/g.

Preferably, 0.8 to 1.3 d(/g) is suitably used in terms of mechanical strength of the molded product.

In addition, the saponified copolymer may further contain small amounts of propylene, isobutyne, α-olefins such as α-octene, α-dodecene, α-octadecene, unsaturated carboxylic acids or their salts, partial alkyl esters, complete alkyl esters, nitrile, It may contain comonomers such as amides/anhydrides, unsaturated sulfonic acids or salts thereof.

(i1) Examples of the fluorine-containing resin include polyvinyl fluoride, vinyl fluoride copolymer, polyvinylidene fluoride,
Vinylidene fluoride copolymer, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer,
Commercially available products such as ethylene chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer can be mentioned as appropriate. . Among them, vinylidene fluoride-based polymers are preferred, and in addition to vinylidene fluoride homopolymers, vinylidene fluoride and α-olefins, such as ethylene, propylene, monofluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene, etc. A copolymer with is suitable.

Furthermore, the polyamide resin (iii) has a number (A) of terminal carfoquinol groups (-COOH) and a terminal substituted amide group (
-C0NRR') [R is a hydrocarbon group having 1 to 22 carbon atoms,
Ro represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

That is, the terminal carboxyl group of a polyamide obtained by polymerization or copolymerization of a lactam having three or more members, an ε-amino acid, or a dibasic acid and a diamine is modified with an N-substituted amide. Usually, mono-substituted amide modification (R' is a hydrogen atom) is practical, but di-substituted amide modification may also be used.

To produce the polyamide resin of the present invention, polyamide raw materials are subjected to polycondensation in the presence of (1) a monoamine having 1 to 22 carbon atoms, (2) a monoamine having 1 to 22 carbon atoms, and a monocarboxylic acid having 2 to 23 carbon atoms.

Specifically, the above polyamide raw materials include lactams such as ε-caprolactam, ethyne tractam, capryllactam, lauryllactam, α-pyrrolidone, α-piperidone, 6-aminocaproic acid, 7-aminononanoic acid, and 9-aminononane. acids, ω-amino acids such as II-aminoundecanoic acid, adipic acid, glutaric acid, pimelic acid, superic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadionic acid, hexadecadionic acid, hexadecenedioic acid, eico Sandionic acid, eicozadienedionic acid, diglycolic acid, 2,2,4. - dibasic acids such as trimethyladipic acid, xylylene diamic acid, 1.4 cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, hexamethylene diamine, tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 22.4
(or 2.4.4)-trimethylhexamethylene diamine, bis-(4,4'-aminone chlorohexyl) methane, diamines such as methaquinlylene diamine, and the like.

Examples of monoamines having 1 to 22 carbon atoms include methylamine,
Ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tocodylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecyl amines, aliphatic monoamines such as octadersine amine, eicosylamine, tocodylamine, cycloaliphatic monoamines such as cyclohexylamine, methylcyclohexylamine, aromatic monoamines such as benzylamine, β-phenylethylamine, N, N - Symmetrical secondary amines such as N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, N,N-hexylamine, N,N-dioctylamine, NN-didecylamine, N- Methyl-N-ethylamine, N-methyl-N
Butylamine, N-methyl-N-todenolamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecylamine, N-ethyl-N-octadecylamine, N-propyl-N-hexadenylamine, N- Examples include hybrid secondary amines such as methyl-N-cyclohexylamine and N-methyl-N-benzylamine.

In addition, examples of monocarboxylic acids having 2 to 23 carbon atoms include acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid , aliphatic monocarboxylic acids such as arachidic acid, behenic acid, cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid, methylcyclohexanecarboxylic acid,
Examples include aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid, and phenylacetic acid.

In addition to the above monoamine or monoamine and monocarboxylic acid, if necessary, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
Decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, hexadecamethylene diamine, octadecane diamine, 2,2,4 (or 2,4.4)-)listerhexamethylene diamine Aliphatic diamines, such as cyclohexane diamine, methylcyclohexane diamine,
Diamines such as alicyclic diamines such as bis-(44゛-aminochlorohexyl)methane, aromatic diamines such as xylylene diamine, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and sperine. Acid, azelaic acid, sebacic acid, undecanedioic acid, todecanoic acid, tridecanoic acid, tetradecadionic acid, hexadecadioic acid, hexadecenedioic acid, octadecadionic acid, octadecenedioic acid, eicosandioic acid,
Eicosenedionic acid, docozanedionic acid, 2,2.4-
aliphatic dicarboxylic acids such as 1-dimethyladipic acid, 1
．． Dicarboxylic acids such as alicyclic dicarboxylic acids such as 4-isochlorohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and quinrylenenocarboxylic acid may also be present.

The reaction for producing the polyamide resin of the present invention may be started in accordance with a conventional method using the polyamide raw materials described above, and the carboxylic acid and amine may be added at any time from the start of the reaction to the start of the reaction under reduced pressure. It can be added at this stage. Also, even if carboxylic acid and amine are added at the same time,
You can also add them separately.

The amount of carboxylic acid and amine to be used is 2 to 20 moq 1 mol, preferably 3 to 19 meq 1 mol, respectively, per 1 mol of polyamide raw material (1 mol of monomer or monomer unit constituting the repeating unit) as the amount of carfoquinol group and amino group. (The equivalent of amino J1 is defined as the amount of amino group that reacts with 1 equivalent of carboxylic acid in a ratio of 1:1 to form an amide bond as 1 equivalent).

If this amount is too small, it will not be possible to produce a polyamide resin having the effects of the present invention. On the other hand, if the amount is too high, it becomes difficult to produce a polyamide with high viscosity, and the physical properties of the polyamide resin are adversely affected.The reaction pressure is preferably 4.00 Torr or less at the end of the reaction. It is preferable to perform this at a pressure of 300 Torr or less. If the pressure at the end of the reaction is too high, the desired relative viscosity cannot be obtained. There is no disadvantage to having low pressure.

The reaction time under reduced pressure is preferably 0.5 hours or more, usually 1 to 2 hours.

The hydrocarbon method represented by R or R' in the substituted amide group (, -CONRR') that the polyamide resin of the present invention has at the terminal includes a methyl group, an ethyl group, a propyl group,
Butyl group, pentyl group, heginyl group, heptyl group, octyl group, 2-edylhequinol group, nonyl group, decyl group,
aliphatic hydrocarbon groups such as undenol group, dodecyl group, tridenol group, tetra-radecyl group, tetradenlene group, bentadenol group, hexadecyl group, bentadenol group, octadecyl group, octadesolene group, eikonol group, toconol group, noclohexyl group, methylcyclohexyl group,
Examples include alicyclic hydrocarbon groups such as a cyclohexynylmethyl group, and aromatic hydrocarbon groups such as a phenyl group, a tolyl group, a hensyl group, and a β-phenylethyl group.

-CON of terminal -COOI-I group of polyamide resin
The conversion ratio to RR'' groups is controlled by the presence of an amine or an amine and a carboxylic acid during the production of the polyamide resin, but in the present invention, the degree of conversion is 5 mol% or less of the COOH groups. Preferably, 0 mol% or more of IO is converted to -CONRR' groups, and the amount of unconverted -C00I-I groups is 50μ
eq/g・polymer or less, preferably 40μeq/g・
It is desirable that the amount is less than or equal to the polymer. If the degree of this conversion is small, the effects of the present invention cannot be expected. On the other hand, increasing the degree of conversion is not disadvantageous in terms of physical properties, but it makes production difficult, so it is best to limit the amount of unmodified terminal carboxyl groups to lμsq/g polymer. .

"The hydrocarbon groups represented by R and R' in the -CONRR' group are obtained by hydrolyzing the polyamide resin using hydrochloric acid,
Measured by gas chromatography. -COOH group can be obtained by dissolving polyamide resin in benzyl alcohol and OI
Measure by titration with N caustic soda.

As the terminal group of the polyamide resin, the above-mentioned one CON
In addition to the RR' group, there are the COOJ-I group and the -NH2 group derived from the polyamide raw materials mentioned above.

The terminal amino group may be modified or unmodified, but it is preferably modified with a hydrocarbon as indicated in "-" because of its good fluidity and melt thermal stability.

N H2 groups are measured by dissolving a polyamide resin in phenol and titrating with 005N hydrochloric acid.

The relative viscosity "ηred" of the polyamide resin of the present invention is J
1% concentration in 98% sulfuric acid according to IS K 6810,
The value measured at a temperature of 25°C is 2 to 6, preferably 2 to 5. If the relative viscosity is too low, it will be difficult to form into strands and chips, resulting in inconvenience in manufacturing. On the other hand, if it is too high, moldability will deteriorate.

The blending ratio of (i), (ii), and (iii) is selected from (i)/(iii) 98/2 to 2/98, preferably 9515 to 10/90, on a weight basis.

When (i)/(iii) is 98/2 or more, the effect of improving the impact strength of saponified ethylene-vinyl acetate copolymer cannot be obtained, and conversely, when it is 2/98 or less, polyamide-based The oxygen barrier properties and rigidity improvement effect of the resin are low, and it is not practical.

(i1) is IOpp for [(i) ten (iil)]
If it is less than the lower limit, it is difficult to obtain the long-run effect of the present invention, and if it is less than 3% by weight, smearing may occur during extrusion or the film may deteriorate. transparency is reduced.

In the present invention, the composition of (() saponified ethylene-vinyl acetate copolymer, (ii) fluorine-containing resin, and (iii) polyamide resin) can be melt-molded into pellets, films, notebooks, containers, fibers, rods, etc. Molded into pipes and various molded products.

These crushed products (such as when recycled products are reused) and pellets are often used again for melt molding. As the melt molding method, extrusion molding ('I'-die extrusion, inflation injection extrusion, blow molding, melt spinning, profile extrusion) and injection molding are mainly employed.

The melt molding temperature is often selected from the range of 150 to 300°C, more specifically, the extruder discharge section temperature of 160 to 290°C and the screw compression section temperature of 150 to 270°C. ”
The two-color injection molding method is a general injection molding method (J or two-color molding,
Inno”.

This method includes compression blow molding, etc., and can produce molded products with good dimensional accuracy.

In melt molding, in addition to the three types of resins mentioned above, plasticizers (polyhydric alcohols, etc.), stabilizers, surfactants, crosslinking substances (epoquine compounds, polyvalent metal salts, inorganic or organic polybasic acids) or its salts), fillers, colorants, fibers as reinforcing agents (glass fibers, carbon fibers, etc.), etc. can be blended in appropriate amounts. In addition, other thermoplastic resins can be blended in appropriate amounts, such as polyolefins (low, medium, and high density polyethylene, isotactic polypropylene, ethylene-propylene copolymer, ethylene-propylene copolymer, etc.). Ene copolymer, copolymer of ethylene and α-olefin having 4 or more carbon atoms, ethylene =
Vinyl acetate copolymer or its saponified product, ethylene-acrylic acid ester copolymer, ionomer, polybutene,
modified polyolefins, polyamides, such as nylon 6/66 copolymer, polyvinyl chloride, polyvinylidene chloride, polyester, borisdyrene, polyacrylic Examples include polyvinyl alcohol, polyacetal, and melt-moldable polyvinyl alcohol resin.

When employing extrusion molding as a melt molding method, not only the composition of the present application is used for molding, but also the composition and other thermoplastic resins are melted separately, and a compiling adapter or die is used. Coextrusion with bonding inside or outside the die is also often performed. Furthermore, the composition of the present invention can also be extrusion coated onto a base film such as Plastix Filno 1, metal foil, paper, or the like.

As the mating resin for lamination, polyamide resins such as nylon-6 and nylon-6,6, polyester resins, etc. are often used.

Of course, ordinary thermoplastic resins other than those mentioned above, such as polycarbonate, vinyl chloride resin, acrylic resin, styrene resin, vinyl ester resin, vinylidene chloride resin, polyester resin T-mer, polyurethane elastomer In addition to polyacetal, chlorinated polyethylene, and chlorinated polypropylene, any of the above-mentioned polyolefin resins may be used.

The layer structure is that the layers of the molded product obtained from the composition are A (A,, Δ
.

), the other resin layer is B (B ,, r321., ), and the adhesive layer provided as necessary is C, the film,
If it is a notebook or a hole, it has not only a two-layer structure of A/B, but also A/B/C, B/A/B 1B +/
B 2 / A SB / A + / A 2, A /
B/Δ/ 13 / A 1A 2 / A + /
T3/A1/A2, A/C/B.

Δ/C/B/C/A, B/C/A/C/B, A/C/1
Any configuration such as 3/C/A/C/I3/C/A is possible, and if it is filament-like, A, B
is bimetal type, core (C) sheath (B) type, core (B) - sheath (
Any combination such as A) type or eccentric core-sheath type is possible. Further, either or both of A and B may be blended with the other resin, or a resin may be blended to improve the adhesion between the two resins.

Molded products after melt molding, coextrusion molded products, and melt coated products are subjected to heat treatment, cooling treatment, rolling treatment, -axial or biaxial stretching treatment, printing treatment, ), lylaminate treatment, solution or melt coating treatment as necessary. , bag making processing, searching processing, box processing, dicob processing, split processing, etc. can be performed.

[Effects] Thus, the composition of the present invention significantly improves the problem of gelling during the high-temperature melt molding process, improves long-run performance, and reduces gelling to prevent contamination of gelled substances into the melt. In addition, burning of the resin and moss are drastically reduced, and their adhesion to the screen and machine wall is reduced, which also greatly contributes to long-run performance. The resulting molded product, for example, a film, can be of good quality with less physico-eye. Such an effect greatly affects the quality of multilayer structure molded products using the present composition, so its usefulness is extremely large.

[Function] The molded products obtained from the composition of the present invention can be used for various purposes such as various packaging films including food packaging, containers, bottles, food trays, sheets, and various equipment parts. It is possible.

[Example] Next, the resin composition of the present invention will be further explained with reference to Examples. Hereinafter, "parts" and "%" are expressed on a weight basis unless otherwise specified.

Production of polyamide resin Six types of polyamide resins were produced using the following method.

200f! ε-Turniplactam 6 in the autoclave of
0 kg, water 1.2 kg, and the amounts of monoamines and carboxylic acids shown in Table 1 below, closed the tank in a nitrogen atmosphere, heated it to 250°C, and reacted under pressure for 2 hours with stirring. The pressure was gradually released to the pressure shown in Table 1 below, and the reaction was carried out under reduced pressure for 2 hours.

After the pressure was restored to normal pressure by introducing nitrogen, stirring was stopped and the strands were taken out and made into chips. Unreacted monomers were extracted and removed using boiling water and dried.

Relative viscosity of the obtained polyamide resin, terminal -C O O
Amount of H groups, terminal −N I{ , groups and ratio of the number of terminal 100 (B) x I 0 0. % by mole] are shown in Table 1.

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1 to 0 Mi: ~ to 8 products to 1 to ω to ω to +r/, 1 to: to 1 self? am, @ ■[Two to...sire~ Mokaichiichi no R Ki, entry awnmo Saponified products of ethylene-vinyl acetate copolymer Four types of saponified products were prepared as shown in Table 2.

Furthermore, the following fluorine-containing resin was prepared.

B-1: Vinylidene fluoride-hexafluoropropylene copolymer (copolymerization weight ratio 60/40) B-2: Tetrafluoroethylene-hexafluoropropylene copolymer (copolymerization weight ratio 89/II) Examples 1-6. Reference Examples 1 to 3 (i), (ii), (iii) as shown in Table 3
0) Using a predetermined amount of each component and using an extruder equipped with a T-die, a film with a thickness of 30 μm was produced under the following conditions.

Extruder: 40mm diameter extruder Screw: full flight screw L/D=28, compression ratio 38 T-die width: 400mm Extrusion temperature feed zone Combre Sonnyon Zone metering zone Thailand Screw rotation speed: 6 Orpm Film tension speed: 3 (im/min The results are shown in Table 3.

<Case I> 180°C 200°C 230°C 220°C Case ■〉 260℃ 275°C 280°C 270℃ ~23 pulse

Claims (1)

[Claims] (i) Saponified ethylene-vinyl acetate copolymer (ii)
Fluorine-containing resin and (iii) number of terminal carboxyl groups (-COOH) (A
) and the number (B) of terminally substituted amide groups (-CONRR') [where R is a hydrocarbon group having 1 to 22 carbon atoms, R' is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms] A resin composition with improved melt moldability, comprising a polyamide resin satisfying the following formula: (B)/((A)+(B))×100≧5.