JPH08259804A - Impact-resistant resin composition - Google Patents

Abstract

PURPOSE: To obtain a composition excellent in mechanical properties such as impact resistance, gas-barrier property, thermoformability, recovering characteristics and hot-water-retort resistance and also having excellent stress- crack resistance against an organic liquid such as gasoline. CONSTITUTION: This is a resin composition obtained by compounding a polyalcohol polymer (A) obtained by reducing a polyketone consisting of a carbon monoxide-ethylene copolymer and a thermoplastic resin (B) other than a polyolefin resin and having a weight ratio of the component A to the component B of 99/1 to 1/99. Another resin composition is obtained by compounding 100 pts.wt. of the obtained resin composition with 0.1-50 pts.wt. of a modified thermoplastic resin (C) having a functional group reactive with the polyalcohol A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having improved mechanical properties such as impact resistance.

[0002]

2. Description of the Related Art Polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer has a good gas barrier property, but alone has insufficient mechanical properties and the like. Further, in a multilayer structure with polyolefin or the like, there are problems in terms of secondary processability, that is, stretchability and thermoformability.

[0003]

The present invention was devised in order to overcome the above-mentioned drawbacks of the prior art, and is a polyalcohol having improved stretchability, thermoformability and mechanical properties. It is to provide a system composition.

[0004]

The above object is to provide a resin composition comprising a polyalcohol polymer (A) and a polyolefin (B), or a functional group capable of reacting with the polyalcohol (A). It is achieved by providing a resin composition containing a modified thermoplastic resin having:

In the present invention, the polyalcohol is a polyalcohol obtained by reducing a polyketone comprising a carbon monoxide-ethylene copolymer, and in particular, the repeating unit represented by the formula (I) is 80% or more. The polyalcohol containing is preferable from the viewpoint of gas barrier properties, mechanical properties, and moldability.
The content of the repeating unit is more preferably 90% or more, particularly preferably 95% or more, and most preferably 97% or more.

[0006]

Embedded image

The above polyketone is a carbon monoxide-ethylene type copolymer, and the carbon monoxide-ethylene type copolymer is obtained by copolymerizing carbon monoxide and ethylene, or Representative examples include those obtained by copolymerizing carbon oxide and ethylene as a main component with an unsaturated compound other than ethylene. Here, as the unsaturated compound other than ethylene, an olefin having 3 to 12 carbon atoms,
Examples thereof include dienes having 4 to 12 carbon atoms, vinyl esters, aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid salts, and aliphatic unsaturated carboxylic acid esters. Examples of the copolymer include a random copolymer and an alternating copolymer, and an alternating copolymer having a high carbonyl group content is preferable.

Examples of the olefin having 3 to 12 carbon atoms include propylene, butene-1, isobutene, pentene-
1,4-methylpentene-1, hexene-1, octene-1, dodecene-1, styrene and the like can be mentioned, but propylene, olefin having 4 to 8 carbon atoms, or propylene and olefin having 4 to 8 carbon atoms. A combination system with is preferred. Examples of the diene having 4 to 12 carbon atoms include butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate and the like. Also,
Examples of the aliphatic unsaturated carboxylic acid, its salt and its ester include acrylic acid, methacrylic acid, maleic anhydride,
Maleic acid, itaconic acid, acrylic acid ester, methacrylic acid ester, maleic acid monoester, maleic acid diester, fumaric acid monoester, fumaric acid diester, itaconic acid monoester, itaconic acid diester (as these esters, methyl ester, ethyl ester Alkyl ester such as ester), acrylate,
Examples thereof include maleic acid salts and itaconic acid salts (these salts include monovalent or divalent metal salts).

The polyketone can be produced by known methods, for example, US Pat. No. 2,495,286 and JP-A-53-128690 and JP-A-53-128691.
JP-A-59-197427 and JP-A-61-912.
26, JP-A-62-232434, JP-A-62-5.
3332, JP-A-63-3025, JP-A-63-1
05031, JP-A-63-154737, JP-A-1
The methods described in JP-A-149829, JP-A-1-201333, JP-A-2-67319 and the like can be mentioned, but the method is not particularly limited thereto. Next, as a method for obtaining a polyalcohol by reducing the carbonyl group in the polyketone, a method of reducing a part or all of the carbonyl group in the polyketone with hydrogen, for example,
JP-A-1-149828, JP-A-2-232228
JP-A-5-339367, JP-A-6-49203
And a method of treating a part or all of the carbonyl group in the polyketone with a metal hydrogen compound to reduce the polycarbonyl, for example, the method described in JP-A-1-204929.

The intrinsic viscosity [η] of the polyol is 0.2 to
It is 5 dl / g, preferably 0.5 to 3 dl / g (value measured by Ostwald viscometer at 30 ° C. in a mixed solvent of 15% by weight of water-85% by weight of phenol).

In the present invention, only one polyalcohol may be used, but it is preferable to use two or more different polyalcohols. In the case of a mixture of two or more kinds, the respective polyalcohols to be mixed may be out of the above range, and it is necessary that they are within the above range as a mixture.

The thermoplastic resin (B) excluding the polyolefin resin of the present invention includes polyamide (PA), polyester (PES), polycarbonate (PC), polystyrene (PS), polyurethane (PU), polyvinyl chloride (PVC). ), Polyvinylidene chloride (PVDC), polyvinyl acetate (PVAC), polybutadiene, polyisoprene, a block polymer of an aromatic vinyl monomer (such as styrene) and a diene, and a moisture resistant thermoplastic resin such as a hydrogenated product of the block polymer. And so on. Further, the kind of the thermoplastic polymer is appropriately selected depending on the required properties and application.

The blend weight ratio of the polyalcohol polymer (A) and the thermoplastic resin (B) is 1/99 to 99 /.
1, more preferably 5/95 to 95/5. 1/99
If it is less than the above, effective properties are not exhibited in terms of barrier property, hydrophilicity and the like. On the other hand, when it is 99/1 or more, the effect of improving the moldability is lost.

Examples of the modified thermoplastic resin (C) having a functional group capable of reacting with the polyalcohol (A) in the present invention include a maleic anhydride group capable of reacting with a polyalcohol polymer, an epoxy group, and a silanol group. Examples thereof include modified thermoplastic resins having at least one functional group selected from the group consisting of carboxylic acid and boronic acid groups. Examples of the thermoplastic resin as a raw material include the above-mentioned thermoplastic resin (B) and a polyolefin-based resin, and examples of the polyolefin-based resin include polyolefin {polyethylene (high, medium, low density polyethylene,
Linear low-density polyethylene), ethylene-propylene copolymer, polypropylene (PP), etc.}, ionomer (IO), ethylene-vinyl acetate copolymer (EVA),
Ethylene-acrylic acid copolymer (EAA), ethylene-
Examples thereof include acrylic acid ester copolymer (EEA), and one or more of these can be used.

Addition amount (weight) of modified thermoplastic resin (C)
Is component (C) / component {(A) + (B)} = 0.1-5
It is 0, and preferably 1 to 30. By using the modified thermoplastic resin (C) within the above range, the compatibility is further improved, the thermal stability is also improved, and the generation of seeds can be suppressed.

The method of blending the polyalcohol-based polymer (A) with the thermoplastic resin (B) and the modified thermoplastic resin (C) is not particularly limited, but the polyalcohol (A) is preceded. A method of melt-blending the thermoplastic resin (B) and the modified thermoplastic resin (C) after melting,
Alternatively, a method in which the polyalcohol (A) and the thermoplastic resin (B) are first melt-blended and then the modified thermoplastic resin (C) is melt-blended, (A) and (B), or (A), ( A method in which B) and (C) are melt-blended at the same time is included. As the blending method, known methods such as a Banbury mixer method and a melt blending method using a single-screw or twin-screw extruder can be adopted.

Polyalcohols include plasticizers, hydrotalcites, higher fatty acid salts and other recovery agents, ultraviolet absorbers, antistatic agents, pigments, antioxidants, lubricants, slip agents, and coloring agents, as long as they do not interfere with the present invention. You may mix agents.
Further, a polymer such as an ethylene-vinyl alcohol copolymer, a polyamide, a super absorbent resin, or a polyolefin may be blended within a range not impeding the present invention.

By laminating a thermoplastic polymer layer on at least one side of the above-mentioned resin composition layer, a multilayer structure which is a preferred embodiment can be obtained. Here, the thermoplastic polymer is not particularly limited as long as it improves the moisture resistance and mechanical properties of the resin composition layer, but is not limited to polyolefin (polyethylene (high, medium, low density polyethylene, linear chain Low density polyethylene), ethylene-propylene copolymer, polypropylene (PP), etc.}, ionomer (I
O), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-acrylic acid ester copolymer (EEA), polystyrene (P
S), and further polyesters (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamides, polycarbonates, polyvinyl chloride, polyvinylidene chloride, polyurethanes, polyacetals, vinyl alcohol-based polymers such as ethylene-vinyl alcohol copolymers. (EVOH) and the like are also included. Moreover, the above-mentioned polyalcohol, polyketone, etc. are mentioned as a thermoplastic polymer. Further, the kind of the thermoplastic polymer is appropriately selected depending on the required properties and application.

The multilayer structure is formed by a known method such as co-extrusion, co-injection, extrusion coating, and scraps of these molded articles can be reused. When the scraps are reused, the present invention can be used. The resin composition may be blended in the scrap, or the component (A), (B) or the component (C) used in the present invention may be blended in the scrap.

When a multilayer structure is obtained, it is often preferable to interpose an adhesive resin layer between the polyalcohol composition layer of the present invention and the thermoplastic polymer layer because both layers can be firmly adhered. The adhesive resin is not particularly limited as long as it can firmly bond both layers, but an unsaturated carboxylic acid or its anhydride (maleic anhydride, etc.) is used as an olefin polymer or copolymer. Polymer [polyethylene {low-density polyethylene, linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (SLDPE)}, ethylene-vinyl acetate copolymer,
Ethylene- (meth) acrylic acid copolymer, ethylene-
(Meth) acrylic acid ester (methyl ester or ethyl ester) copolymer, polypropylene, etc.] grafted, hydrogenated styrene-butadiene copolymer acid anhydride (maleic anhydride, etc.) modified product, liquid butadiene acid Diene polymer acid anhydride modified products such as anhydride modified products and acid anhydride modified products of ethylene-propylene-diene copolymer are preferably used.

The layer structure of the multilayer structure is as follows: resin composition layer / thermoplastic polymer layer, resin composition layer / thermoplastic polymer layer / resin composition layer, thermoplastic polymer layer / resin composition layer /
Thermoplastic polymer layer, thermoplastic polymer layer / resin composition layer /
Scrap recovery layer / thermoplastic polymer layer, thermoplastic polymer layer / scrap recovery layer / resin composition layer / scrap recovery layer / thermoplastic polymer layer, or the adhesive resin described above between at least one of these layers Examples include those in which layers are interposed.

The multi-layer structure obtained from the above-mentioned resin composition of the present invention is used for packaging materials such as foods, pharmaceuticals, medical equipments, clothes, etc., which are required to have gas barrier properties, and particularly gas barrier properties and mechanical strength. It is useful in non-food fields such as pipes and tanks where impact resistance is required.

In particular, the multilayer structure of the present invention comprises: 1) a tank for organic liquids, a pipe, a hot water pipe for floor heating, 2) a cup requiring recoverability, impact resistance, and heat resistant water retort,
When used in bottles, 3) films and sheets that require stretching and shrinkability, the performance is remarkably exhibited.

Conventionally, fuels (gasoline, etc.), pesticides, organic liquids such as organic liquids are used as tanks and pipes. Permeability of organic liquids, for example, reduction of impact strength and stress cracking due to use of gasoline, especially methanol mixed gasoline. As a result, the composition of the present invention has a significant improvement effect on the problem that the barrier property is greatly deteriorated or liquid is leaked.

Burrs and scraps generated during molding of cups and bottles account for 30 to 50%, and it is difficult to dispose of them and incinerate them due to global environmental problems, etc., and it is necessary to collect and reuse them because of the need to reduce manufacturing costs. It has been demanded. Therefore, by using the composition of the present invention, an effect of improving abnormal flow during molding (nonuniform film surface) during recovery and reuse and deterioration of transparency is recognized.

Further, the resin composition of the present invention is effective for improving various required performances such as low temperature impact resistance of cups and bottles, and hot water retort property.

On the other hand, examples of the film and sheet applications requiring stretching and shrinkability include a barrier shrink film, a barrier skin pack film, and a thermoforming barrier sheet. As for shrink film and skin pack film, stretchability and stretching speed are not sufficient in terms of stretchability, so uneven stretching and heat shrinkability cannot be obtained. There is a problem that abnormalities such as cracks and unevenness occur on the side surface of the thermoformed container due to defects. However, these problems can be remarkably ameliorated, probably because the composition of the present invention has flexibility. This is clear from the description of the examples given later.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following Synthesis Examples and Examples, "%" means "% by weight" unless otherwise specified.

[0029]

【Example】

Example 1 A polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer (A) {comprising 96% of a repeating unit represented by the formula (I) and other 4%, an intrinsic viscosity [η]
= 0.8 dl / g} 90 parts by weight, 6/12 polyamide (B) (melt index = 1.3 g / 10 minutes, 6 /
12 = 50/50% by weight) 10 parts by weight, and then pelletized under the following conditions. Extruder used: Segment type lab twin screw extruder (25
mm diameter) Screw shape: C type (strong kneading type) Screw rotation speed: 230 rpm Discharge rate: 0.6 Kg / h

The pellets were applied to a 4-type 5-layer coextrusion multi-layer pipe molding device to prepare a multi-layer pipe. The outermost layer (12 nylon layer) was 450μ, the adhesive resin layer was 50μ each, the 6 nylon layer was 100μ, the polyalcohol composition layer was 150μ, and the innermost layer (6 nylon layer) was 250μ. is there. Attach a metal fitting to the end of the obtained pipe, wind it in a loop at R (radius) = 30 cm, fill it with gasoline, and under the conditions of 40 ° C and 65% RH, 1
After leaving for a year, no cracks or deterioration of gasoline barrier properties were observed. As an acceleration test, the body of the pipe is sliced into rings, and the sliced pipe is spread with a cylindrical jig having an outer diameter that is 10% longer than the inner peripheral length of the pipe so that 10% tensile elongation can be added (10 % Tensile elongation), immersed in gasoline containing 40%, 15% methanol for 3 hours, and evaluated for stress cracking properties, but no cracks were observed. The gasoline permeability of the pipe was 0.2 g / m ² . It was a day.

Example 2 A polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer (96% of repeating units represented by the formula (I), and 4% of others, and an intrinsic viscosity [η ]
= 0.8 dl / g} 97 parts by weight, 6/12 polyamide (B) (melt index = 1.3 g / 10 minutes, 6 /
12 = 50/50% by weight) and 3 parts by weight of maleic anhydride modified polypropylene (Mitsui Petrochemical Admer QF5
00) 10 parts by weight were mixed and pelletized in the same manner as in Example 1. The pellets were charged into a 3 type 5 layer coextrusion device,
A multilayer sheet (polypropylene resin layer, adhesive resin layer / polyalcohol composition layer / adhesive resin layer / polypropylene resin layer) was prepared. The structure of the sheet is the polypropylene resin layer of both outermost layers (Mitsui Petrochemical Noblen PY22
0) is 800μ, and an adhesive resin layer (Mitsui Petrochemical Adma-QF500 maleic anhydride modified polypropylene)
50 μm each, and further an intermediate layer (polyalcohol composition layer)
Is 50 μ. The sheet was subjected to a vacuum pressure air thermoforming machine (stretching speed 9 × 10% / min.) And molded at 180 ° C. As a result, the molded product was free from cracks, unevenness, uneven thickness, and had good appearance and transparency. After filling this container with water, heat sealing the upper lid, and the surroundings, a retort device (Hisaka Seisakusho Co., Ltd., sterilization test device R for high temperature and high pressure cooking)
CS-40ORTGN) was used to perform sterilization treatment at 120 ° C. After the sterilization treatment, the cup was not observed to have poor transparency (whitening), poor appearance, and poor morphology.

Example 3 The polyalcohol composition used in Example 2 was applied to a Class 3 pentasodium coextrusion machine to prepare a multilayer sheet. The composition of the sheet is such that both outermost layers {EVA resin layer (DuPont Mitsui Chemicals: EVA-Flex EV-340)} are 300μ each and adhesive resin layer (Mitsui Petrochemical Admer VF-600) is 50 each.
μ, and the intermediate layer (polyalcohol composition layer) is 50 μ
Is. The obtained sheet was subjected to a pantograph-type biaxial stretching machine, and simultaneously biaxially stretched at 70 ° C. at a stretching ratio of 3 × 3. The obtained multilayer heat-shrinkable film was free from cracks, unevenness, uneven thickness, and had good appearance and transparency. When the humidity of this film was adjusted to 20 ° C.-100% RH and the gas barrier property was measured (10/50 type manufactured by Mocon Co.), the oxygen permeability was 50 cc. 20 μ / m ² . 24 hr. Atm and good gas barrier property were exhibited. Further, when the heat shrinkability at 70 ° C. was measured, it showed an area shrinkage of 50%.

Example 4 Polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene-propylene copolymer (the molar ratio of ethylene / propylene is 90/10, represented by the formula (I)). It is composed of 96% of repeating units and 4% of others, 90 parts by weight of intrinsic viscosity [η] = 0.9 dl / g, thermoplastic polyurethane (B) (melt index = 4.3 g / 1
0 minutes) 10 parts by weight were mixed and pelletized in the same manner as in Example 1. The pellets were put into a three-kind five-layer co-extrusion direct blower, and a multi-layer bottle (polypropylene resin layer,
Adhesive resin layer / polyalcohol composition layer / adhesive resin layer / polypropylene resin layer) was prepared. The bottle is composed of polypropylene resin layers on both outermost layers (Mitsui Petrochemical
No-Blen PY220) is 300 μ each, the adhesive resin layer (Mitsui Petrochemical Adma-QF500 maleic anhydride modified polypropylene) is 50 μ each, and the intermediate layer (polyalcohol composition layer) is 50 μ, and the capacity is 100.
It is 0 ml. The bottle was filled with water and the drop impact was measured at 0 ° C. As a result, the bag was not broken even if it was 2 m or more.

[0034]

Industrial Applicability The resin composition of the present invention is excellent in mechanical properties such as impact resistance and gas barrier properties, and is also excellent in thermoformability, recoverability and hot water retort property, and is more resistant to organic liquids such as gasoline. Excellent stress crack resistance.

Claims (2)

[Claims] 1. A polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer and a thermoplastic resin (B) other than a polyolefin resin, and a component (A) / component. The weight ratio of (B) is 99/1
~ 1/99 resin composition. 2. A functional group capable of reacting with a polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer, a thermoplastic resin (B) other than a polyolefin resin and (A). Made of a modified thermoplastic resin having a ratio of (A) / (B) of 99 /
1 to 1/99, and component (C) / component {(A) +
A resin composition in which the weight ratio of (B)} is 0.1 to 50/100.