JPH0651817B2 - Resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyamide resin, etc.
Of the thermoplastic resin and the saponified product of the ethylene-vinyl acetate copolymer, the composition having remarkably improved compatibility.

[0002]

2. Description of the Related Art Saponified ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVOH) and other thermoplastic resins (excluding polyolefin, but thermoplastic resins excluding polyolefin are simply It may be called a plastic resin.) The blend composition has a characteristic physical property. In particular, a blend composition may be used in place of the thermoplastic resin layer or the EVOH layer during multi-layer coextrusion molding of various thermoplastic resins and EVOH, or a layer of the blend composition may be formed between the thermoplastic resin and the EVOH layer. It is possible to improve the interlayer adhesive force by providing the. Molded products such as films, sheets and bottles obtained by melt-extruding the blend composition alone and, if necessary, stretching and / or heat-treating have excellent gas barrier properties and mechanical properties. The characteristics of such blended compositions of various thermoplastic resins and EVOH have been known in the past, but these compositions generally have poor compatibility, and when films, sheets, bottles, etc. are formed by extrusion molding, they are non-uniform. It is known that phase-separated foreign matter is liable to be generated, and especially when operated for a long time, the foreign matter is increased and the appearance is significantly impaired. Thus, in reality, the blend composition of various thermoplastic resins and EVOH cannot be extruded practically at all, or can be operated only for a short period of time, despite its excellent characteristics.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve such poor compatibility, and an object thereof is to obtain a molded article having a beautiful appearance.

[0004]

Means for Solving the Problems The above object is to provide the thermoplastic resin (A) and EVOH (B) with an oxide of at least one metal selected from Group I, Group II and Group III of the periodic table .
And at least one compound (C) selected from ethylenediaminetetraacetic acid salt , in an appropriate amount. When molded using this composition, the compatibility of the thermoplastic resin and EVOH is remarkably improved, the appearance is beautiful, and the coextruded product has a high interlaminar adhesive force, or the gas barrier property and the mechanical property are excellent. A molded product can be obtained.

The thermoplastic resin (A) referred to in the present invention means polyamide resin, polyester resin, polystyrene resin, polyvinyl chloride resin, acrylic resin, polyvinylidene chloride resin, polyurethane resin, polyacetic acid. At least one heat selected from the group consisting of vinyl resins, polyacetal resins and polycarbonate resins
Of the plastic resins, polyamide resins and polyester resins are particularly important for the present invention in terms of their effects and practical performance, and then polyvinyl chloride resins and polystyrene resins are also important.

Polyamide-based resins include polycapramide (nylon-6), poly-ω-aminoheptanoic acid (nylon-7) and poly-ω-aminononanoic acid (nylon-).
9), polyundecane amide (nylon-11), polylaurinlactam (nylon-12), polyethylenediamine adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adiba Mido (nylon-6,6), polyhexamethylene sebacamide (nylon-6,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon-8,6), poly Decamethylene adipamide (nylon-10,6), polydodecamethylene sebacamide (nylon-10,8), or caprolactam / laurinlactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurinlactam / Hexamethylene diammonium adipate Polymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer ,
And so on. Among them, the caprolactam / hexamethylene diammonium adipate copolymer (nylon-6 / 66) has a particularly excellent physical property in the blend with EVOH and is particularly important for practical use.

Representative examples of the polyester resin include poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene terephthalate / isophthalate), poly (ethylene glycol / cyclohexanedimethanol / terephthalate), and the like. As a copolymerization component of these polymers, diols such as ethylene glycol, butylene glycol, cyclohexanedimethanol, neopentyl glycol and pentanediol, or isophthalic acid, benzophenone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenylmethane dicarboxylic acid, propylene bis ( Phenyl carboxylic acid), diphenyl oxide dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Those containing dicarboxylic acids such as sebacic acid and diethylsuccinic acid are also included.

Examples of polyvinyl chloride resins include homopolymers of vinyl chloride, and copolymers with vinyl acetate, maleic acid derivatives, higher alkyl vinyl ethers and the like.

Examples of the polystyrene resin include styrene homopolymer, polystyrene obtained by graft-copolymerizing butadiene, a mixture of styrene-butadiene rubber and a styrene-maleic anhydride copolymer.

Further, the saponified product of ethylene-vinyl acetate copolymer (EVOH) (B) referred to in the present invention is any as long as it is obtained by hydrolyzing a vinyl acetate unit in a copolymer of ethylene and vinyl acetate. However, those having poor compatibility with the thermoplastic resin have relatively few ethylene units and a high degree of saponification (hydrolysis) of vinyl acetate units. In particular, the content of ethylene units is 20-50 mol%
And the degree of saponification of vinyl acetate units is 96% or more, especially 9
If 9% or more, the gas barrier property against gases such as oxygen is at the highest level in the thermoplastic resin, and excellent containers can be obtained by using it in combination with polyolifin, so that the present invention is applied. It is especially important as a target.

Furthermore, an oxide of at least one metal selected from Group I, Group II and Group III of the periodic table and ethylenediaminetetraacetic acid salt (C) constituting the composition of the present invention.
Examples of the compound include many compounds, among which oxides such as calcium oxide, magnesium oxide, barium oxide, and zinc oxide, and metals of ethylenediaminetetraacetic acid (group I,
Group II or III) salts are effective. Further, among these compounds, it has been found that compounds containing a metal element of Group II of the periodic table such as magnesium, calcium and zinc act particularly effectively. The metal (group I, group II or group III) salts of ethylenediaminetetraacetic acid include disodium salt, trisodium salt, tetrasodium salt, dipotassium salt, tripotassium salt, tetrapotassium salt, disodium monomagnesium salt, disodium salt. Preferred are monocalcium salt, disodium monomagnesium salt, disodium monoiron salt, disodium monozinc salt, disodium monobarium salt, disodium monomanganese salt, disodium monolead salt, dipotassium monomagnesium salt and the like. . These (C) components are
Used alone or in combination of two or more.

(A), (B) constituting the composition of the present invention
The amount of each component of (C) and (C) is not particularly limited and can be arbitrarily selected according to the purpose. However, from a practical point of view, as the composition ratio of the thermoplastic resin (A) and EVOH (B), a composition having a large amount of either one of the resins exhibits mechanical properties or characteristic properties such as gas barrier property. It is especially important in terms of As a composition containing a large amount of thermoplastic resin, the weight ratio of thermoplastic resin (A): EVOH (B) is 60: 40-9.
9.9: 0.1, especially 70:30 to 99.7: 0.
In the case of a composition containing a large amount of EVOH, the weight ratio of thermoplastic resin (A) to EVOH (B) is 1:99 to 40:60, and particularly 5:95 to 3
It can be said that the range of 0:70 is particularly important in terms of the effect of the present invention. Further, the compound (C) which improves the compatibility.
The addition amount of (A), (B) and (C) has an effect of improving compatibility depending on the types of the components, and does not impair various physical properties such as mechanical properties, transparency and gas barrier property of the composition. The amount is adjusted in the range, but in many cases, the amount is 0.00001 to 10 parts, especially 0.000, relative to 100 parts by weight of the thermoplastic resin (A) and EVOH (B) (A + B).
Used in the range of 1 to 1 part. If it exceeds 10 parts, various physical properties other than compatibility are likely to be impaired, and this is often not preferable. Further, when the component (C) is blended in advance with the thermoplastic resin and / or EVOH, the use effect tends to be high. As an example of blending with EVOH, E
The thing which mix | blended 0.002-0.5 part of (C) component with 100 parts of VOH is mentioned. The effect of improving the compatibility in melt molding of a composition obtained by adding 0.5 parts of this compound and 99.5 parts of a thermoplastic resin is remarkable. In this case, the amount of the component (C) is 0.00001 to 0.0025 part with respect to 100 parts by weight of the thermoplastic resin and EVOH. When the amount of the component (C) is less than 0.00001 part, the effect is generally small. Thus, it can be said that when the component (C) is blended with EVOH, the effect is great even when the addition amount is apparently small.

The blending method for obtaining the composition of the present invention is not particularly limited, and a method of dry blending the three is
Alternatively, the component (C) is preliminarily blended with all or part of the thermoplastic resin or EVOH, and then it is blended with the thermoplastic resin and / or EVOH, and the components (A), (B) and (C) are added. The method for obtaining the composition is arbitrarily selected according to the purpose. Generally, in addition to the method of blending with EVOH as described above, a method of dry blending or a method of blending with a thermoplastic resin in advance can be combined to obtain a particularly remarkable effect of improving compatibility. .

In the present invention, the mechanism by which the compound (C) containing a metal of group I, group II or group III of the periodic table significantly improves the compatibility of the thermoplastic resin and EVOH in melt molding is sufficiently clear. However, it is presumed that the component (C) effectively acts in a state where the rheological effect in the molten system of the thermoplastic resin and EVOH, the chemical action of impurities, etc. are complicatedly combined.

Other conventional additives may be added to the thermoplastic resin for the composition of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, and other polymer compounds, which are used in the present invention. It is possible to blend within a range in which the action and effect are not impaired. The following are specific examples of the additive.

Antioxidants: 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol, 2,2 '. -Methylene-bis (4-methyl-6-t-
Butylphenol, octadecyl-3- (3 ', 5'-
Di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6-t-butylphenol) and the like. UV absorber: Ethyl-2-cyano-3,3
-Diphenyl acrylate, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2- (2
'Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotrial, 2-hydroxy-
4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone etc. Plasticizer: dimethyl phthalate, dimethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc. Antistatic agent:
Pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbowax, etc. Lubricants: ethylene bis stearamide, butyl stearate, etc. Coloring agents: carbon black, phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, red iron oxide, etc. Filler: Glass fiber, asbestos, mica, ballastonite, calcium silicate, aluminum silicate, calcium carbonate, etc.

Examples of means for blending the respective components for obtaining the composition of the present invention include a ribbon blender, a high speed mixer co-kneader, a mixing roll, an extruder and an intensive mixer.

The resin composition of the present invention is a well-known melt extrusion molding machine, compression molding machine, transfer molding machine, injection molding machine,
A blow molding machine, a thermoforming machine, a rotary molding machine, a dip molding machine or the like can be used to mold any desired molded article such as a film, a sheet, a tube or a bottle. The extrusion temperature at the time of molding is appropriately selected depending on the type of resin, the molecular weight, the compounding ratio of the composition, the properties of the extruder and the like, but in most cases, it is in the range of 170 to 350 ° C.

As described above, the resin composition of the present invention exerts unique characteristics in terms of adhesiveness when it is used as one layer of a multi-layer material. However, the thermoplastic resin layer is used as a P or EVOH layer. Is E, the adhesive resin layer is D, and the layer of the composition of the present invention is F, E / F / E, F / E / F, F / F
/ F (F in the intermediate layer has a high content of EVOH), F / D /
E, F / D / E / D / F, P / E / P / F, P / F / D
When a layered structure such as / E / D / F / P or P / F / D / E / D / P is used, a beautiful molded product having high interlayer adhesion and excellent compatibility can be obtained. In such a multilayer molding material, the blend composition of the present invention can be substituted by scrap of the multilayer molding material.

As a multilayer molding method, generally, the number of extruders corresponding to the type of resin layer is used, and the coextrusion molding is carried out in a layered state in which the flows of the resin melted in the extruder are superposed. It is carried out by so-called coextrusion molding. As another method, a multilayer molding method such as extrusion coating or dry lamination can be adopted.
Further, a single molded product of the composition of the present invention, or a multilayer molded product containing the composition of the present invention is subjected to stretching such as uniaxial stretching, biaxial stretching or blow stretching,
It is possible to obtain a molded product having physical properties having further characteristics such as mechanical properties and gas barrier properties. Thus, the molded product obtained from the composition of the present invention has many excellent properties such as strength physical properties and gas barrier properties because not only the blend composition is uniform and the appearance is beautiful, but also the compatibility is good and uniform. It has the following features and its industrial significance is great. Hereinafter, the present invention will be described more specifically by way of examples. The parts mean parts by weight.

[0021]

Example 1 6/66 copolymerized polyamide (66 components 15%, melting point 19)
8 ° C.) 30 parts, EVOH [ethylene unit content 33 mol%, saponification degree 99.9%, melt index (190
C., 2160 g) 1.5 g / 10 minutes] 70 parts, and after dry blending ethylenediaminetetraacetic acid disodium monomagnesium salt powder 0.2 parts, the diameter is 40 mm,
It was charged into an extruder having a full flight type screw having L / D = 24 and a compression ratio of 3.8, and film formation was carried out using a flat die having a width of 550 mm. The film forming temperature is 19 for the extruder.
0 ° -240 ° C, die at 225 ° C, thickness 100μ
The film was wound up with a take-up machine and continuously operated for 6 hours. The obtained film showed uniform and good compatibility, and no phase-separated foreign matter with poor compatibility was observed. A 90 mm square test piece of the obtained film was heated at 85 ° C. for 1 minute by using a biaxial stretching tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and then tripled in length and width at a stretching speed of 5 m / min. It was stretched. Stretching was carried out uniformly, and when this stretched film was fixed to a wooden frame and heat-treated at 110 ° C. in a hot air dryer, a good film having excellent strength and gas barrier properties was obtained.

Comparative Example 1 A film of a mixture of polyamide and EVOH was formed in the same manner as in Example 1 except that ethylenediaminetetraacetic acid disodium monomagnesium salt was not mixed.
Around 30 minutes after the start of operation, a large number of non-uniform phase-separated foreign matters which were not found in Example 1 were observed, the number increased with the passage of time, and the appearance of the obtained film was extremely poor.

Examples 2 to 7 6/66 copolymerized polyamide (PA) shown in Example 1,
EVOH and various (C) components were dry-blended in the ratios shown in Table 1, and then extrusion film formation was carried out in the same manner as in Example 1. The evaluation of the film surface state of the obtained film is also shown in Table 1.

Examples 8 to 10 0.002 parts (Example 8 ), 0.02 parts (Example 9 ) or 0.2 parts of disodium ethylenediaminetetraacetate monomagnesium to 100 parts of EVOH resin in a slurry state in methanol. After addition impregnation with part (Example 10 ), the resin was dried. After dry blending 70 parts of these EVOH resins and 30 parts of the copolyamide resin used in Example 1,
Extrusion film formation was carried out in the same manner as in Example 1. The evaluation of the film surface state of the obtained film is also shown in Table 1.

[0025]

[Table 1]

Note 1) The film surface condition was evaluated according to the following criteria. Excellent: Uniform and good compatibility with no phase-separated foreign matter. Excellent: A uniform and good compatibility is shown, but a small amount of phase-separated foreign matter is slightly observed in molding for a long time. Good: The compatibility is good, but a slight amount of phase-separated foreign matter is observed. Acceptable: The effect of improving compatibility is observed, but a slight amount of phase-separated foreign matter is observed. Note 2) EDTA is an abbreviation for ethylenediaminetetraacetic acid.

Example 11 After 80 parts of polyethylene terephthalate (PET), 20 parts of the EVOH resin used in Example 1 and 0.2 part of ethylenediaminetetraacetic acid disodium monomagnesium salt powder were dry blended, the diameter was 40 mm, L / D = 24,
It was charged into an extruder having a full flight type screw with a compression ratio of 3.8, and film formation was carried out using a flat die having a width of 550 mm. The film forming temperature is 200 to 275 ° C. in the extruder,
The die was heated to 265 ° C., a film having a thickness of 100 μ was wound by a take-up machine, and continuous operation was performed for 6 hours. The obtained film showed uniform and good compatibility, and no phase-separated foreign matter with poor compatibility was observed. 9 of the obtained film
A 0 mm square test piece was heated at 85 ° C. for 1 minute using a biaxial stretching tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and then 5 m / m.
It was stretched 3 times in both length and width at a stretching speed of in. Stretching was carried out uniformly, and when this stretched film was fixed to a wooden frame and heat-treated at 160 ° C. in a hot air dryer, a good film having excellent strength and gas barrier properties was obtained.

[0028] In Comparative Example 2 Example 11, except that no mixture of disodium ethylenediaminetetraacetate one magnesium salt was carried out formation of mixed products of PET and EVOH in the same manner as in Example 11.
Immediately after the start of the operation, a large number of non-uniform phase-separated foreign matters which were not found in Example 11 were observed, the number increased with the passage of time, and the appearance of the obtained film was extremely poor.

Examples 12 to 17 PET, EVOH and various components (C) shown in Example 11 were dry blended in the proportions shown in Table 2 and then
Extrusion film formation was carried out in the same manner as 11 . The evaluation of the film surface state of the obtained film is also shown in Table 2.

Examples 18 to 20 0.002 parts (Example 18 ) and 0.02 parts (Example 1 ) of disodium ethylenediaminetetraacetate monomagnesium were added to 100 parts of EVOH resin in a slurry state in methanol.
9 ) or 0.2 part (Example 20 ) was added and impregnated, and then the resin was dried. Example 11 with 20 parts of these EVOH resins
After dry blending 80 parts of PET used in
Extrusion film formation was carried out in the same manner as 11 . The evaluation of the film surface state of the obtained film is also shown in Table 2.

[0031]

[Table 2]

Example 21 High-impact polystyrene resin (melt flow index 2.2 g / 10 min) (A), ethylene unit content 32.5 mol%, saponification degree 99.9 mol%, melt index 1.4 g / 80 min of 10 min of EVOH (B), ethylenediaminetetraacetic acid disodium (C), and modified ethylene-vinyl acetate copolymer based adhesive resin (D):
A blended product (F) having a ratio of 20: 0.05: 2 was prepared. This blend (F) and the above EVOH (B)
And the adhesive resin (D) are charged into separate extruders, and F / D /
A coextrusion molding of 3 types and 5 layers having a structure of B / D / F (film thickness ratio 15: 1: 2: 1: 15) was carried out to obtain a sheet.
For extrusion molding, B and D had a diameter of 50 mm, an extruder equipped with a single screw of L / D = 25 had a temperature of 180 to 215 ° C., and F had two screws of 100 mm in diameter and L / D = 22. The same direction rotary mesh type twin screw extruder 15
A temperature of 0 to 220 ° C. and a feed block die (width of 1000 mm) at 225 ° C. to obtain a sheet having a thickness of 1000 μ. A good sheet was obtained even after continuous operation for 24 hours, and no phase-separated foreign matter with poor compatibility was observed. The results are shown in Table 3.

[0033] In Comparative Example 3 Example 21, except that no use of disodium ethylenediaminetetraacetate (C), the same procedure as in Example 21 was carried out co-extrusion to obtain a sheet. About one hour after the start of operation, non-uniform phase-separated foreign matter that was not seen in Example 21 was observed, and the number thereof increased with time.

Examples 22 to 26 Polystyrene resin (PS) and EVO shown in Example 21
H, the adhesive resin (AD) and various components (C) are dry blended in the proportions shown in Table 3, and the blended product (F) and the above EVOH (B) and the adhesive resin (D) are separately extruded. Co-extrusion was carried out in the same manner as in Example 21 . The evaluation of the film surface state of the obtained sheet is also shown in Table 3.

Examples 27-29 0.002 parts (Example 27 ) and 0.02 parts (Example 2 ) of disodium ethylenediaminetetraacetate monomagnesium were added to 100 parts of EVOH resin in a slurry state in methanol.
8 ) or 0.2 part (Example 29 ) was added and impregnated, and then the resin was dried. After dry blending the EVOH resin, the polystyrene resin used in Example 21 and the adhesive resin, coextrusion molding was performed in the same manner as in Example 21 . The evaluation of the film surface state of the obtained sheet is also shown in Table 3.

[0036]

[Table 3]

Examples 30 to 35 Polyvinyl chloride (PVC) (A) having an average degree of polymerization of 1300
EVOH (B) and (C) having an ethylene content of 44 mol%, a saponification degree of 99 mol% and a melt index of 5 g / 10 min may be blended with 38 parts of dioctyl phthalate at a ratio shown in Table 4. Mix and use 28-inch inverted L-type calender roll to a thickness of 1 at 215 ° C.
It was formed into a film of 00μ. The obtained film had a good appearance and no phase-separated foreign matter with poor compatibility was observed. Table 4 shows the evaluation of the film surface state of the obtained film.

[0038] Other not using the component (C) in Comparative Example 4 Example 30 was conducted blend formation of polyvinyl chloride and EVOH in the same manner as in Example 30. The film surface of the obtained film was
Uneven phase-separated foreign matter that was not found in No. 30 was observed, and the appearance of the film was poor.

Examples 36-38 0.002 parts (Example 36 ) and 0.02 parts (Example 3 ) of disodium ethylenediaminetetraacetate-magnesium to 100 parts of EVOH resin in a slurry state in methanol.
7 ) or 0.2 part (Example 38 ) and after impregnation, the resin was dried. 20 parts of these EVOH resins and Example 30
After 80 parts of the polyvinyl chloride resin used in Example 1 was dry blended, extrusion film formation was carried out in the same manner as in Example 30 . The evaluation of the film surface state of the obtained film is also shown in Table 4.

[0040]

[Table 4]

[0041]

The compatibility between the thermoplastic resin and EVOH is remarkably improved, and the resulting molded article has a beautiful appearance.
It also has excellent gas barrier properties.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 27/06 LEQ 9166-4J LET 9166-4J 29/04 67/00 LPA 8933-4J LPB 8933- 4J 77/00 LQS 9286-4J 101/00 LSZ 7242-4J // B32B 27/28 102 6122-4F

Claims (6)

[Claims] 1. (A) Polyamide resin, polyester
Resin, polystyrene resin, polyvinyl chloride resin
Oil, acrylic resin, polyvinylidene chloride resin, poly
Urethane resin, polyvinyl acetate resin, polyacetator
From a group consisting of resin and polycarbonate resin
At least one thermoplastic resin selected, (B) an ethylene-vinyl acetate copolymer saponified product, and (C) an oxide of at least one metal selected from Group I, Group II and Group III of the periodic table , and Ethylenediamine
A resin composition comprising at least one compound selected from tetraacetates and containing component (C) in an amount of 0.00001 to 10 parts per 100 parts by weight of the resins (A) and (B). 2. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyamide resin. 3. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyester resin. 4. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polystyrene resin. 5. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyvinyl chloride resin. 6. An ethylene-vinyl acetate copolymer saponified product (B) having an ethylene unit of 20 to 50 mol% and a vinyl acetate unit having a saponification degree of 96% or more. Item 5. The resin composition according to any one of items 5.