JP3497912B2 - Resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition having improved mechanical properties.

[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 is insufficient in flexibility and mechanical properties by itself. 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. The present invention aims to provide a vulcanized 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 comprising a modified polyolefin (C) 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]

[Chemical 1]

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, but the mixture must be in the above range.

In the present invention, it is preferable to use two or more different polyalcohols as the polyalcohol. Here, the different polyalcohol is different from the melt index, the hydrogenation rate of the ketone group and the by-product tetrahydrofuran (T).
It means a polyalcohol differing in at least one of HF) content, ethylene content, and melting point. With respect to the hydrogenation rate of the ketone group, it is desirable that it differs from 1 to 10 mol%, preferably from 2 to 8 mol%, and with respect to the ethylene content, 1 to 40 mol%.
It is desirable that they differ by mol%, preferably 2-35 mol%.
The melt index is 0.1 to 50 g /
10 minutes (190 ° C., 2160 g), preferably 0.2-3
It is desirable to differ by 0 g / 10 minutes. Further, these may be different from each other, or two or all of them may be different from each other. It is desirable that the melting points differ by 1 to 70 ° C, more preferably 2 to 50 ° C. Further, regarding the THF content, it is desirable that they differ by 1 to 10 mol%, preferably 2 to 8 mol%. Further, the addition ratio of these different polyalcohols is arbitrary, but for example, the mixing ratio (weight) when using two kinds of polyalcohol is 1/99 to 99/1, preferably 5/95 to 9
5/5, and more preferably 10/90 to 90/10.

By using different polyalcohols, the addition amount of the polyolefin (B) or modified polyolefin (C) described below, which is required to exhibit the same performance, is larger than that in the case of using one kind of polyalcohol. The width can be reduced, and as a result, the gas barrier property, the transparency and the thermal stability are improved, which is also advantageous in terms of cost.

In the present invention, the polyolefin resin (B) may be a 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 Examples thereof include polymer (EAA) and ethylene-acrylic acid ester copolymer (EEA). Further, the kind of the thermoplastic polymer is appropriately selected depending on the required properties and application.

The blending weight ratio of the polyalcohol polymer (A) and the polyolefin resin (B) is 1/99 to.
99/1, more preferably 5/95 to 95/5. 1
When it is less than / 99, effective performance is 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.

The modified polyolefin resin (C) having a functional group capable of reacting with the polyalcohol (A) in the present invention is a maleic anhydride group, an epoxy group or a silanol group capable of reacting with the polyalcohol polymer. Group and a modified polyolefin having at least one functional group selected from boronic acid groups. Examples of the polyolefin as a raw material include resins having one or more of the above-mentioned polyolefin resins (B).

The amount (weight) of the modified polyolefin resin (C) added is component (C) / component {(A) + (B)} = 0.
It is 1 to 50, and preferably 1 to 30. By using the modified polyolefin (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 polymer (A), the polyolefin resin (B) and the modified polyolefin (C) is not particularly limited, but the polyalcohol (A) is melted in advance. Then, a method of melt-blending the polyolefin (B) and the modified polyolefin (C), or a method of first blending the polyalcohol (A) and the polyolefin (B) and then melt-blending the modified polyolefin (C), Examples include a method in which (A) and (B), or (A), (B) and (C) are melt-blended at the same time. 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 within the range that does not impair 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 the thermoplastic polymer layer on at least one surface 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. For example, the above-mentioned polyolefin (B), further polystyrene (PS), Polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyacetal, vinyl alcohol-based polymer, for example, ethylene-vinyl alcohol copolymer (EVOH) and the like can also be mentioned. 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 multi-layer structure is molded by a known method such as coextrusion, co-injection, extrusion coating, and scraps of these molded products can be reused. When 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 resin 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 (SLDP
E)}, 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 (anhydrous Maleic acid) modified products, acid anhydride modified products of liquid butadiene, acid anhydride modified products of ethylene-propylene-diene copolymers and the like, and diene polymer acid anhydride modified products and the like are preferably used.

The layer structure of the multilayer structure includes 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 multilayer structure obtained from the above-mentioned resin composition of the present invention is used for packaging materials such as foods, pharmaceuticals, medical equipments, clothing, etc., which require gas barrier properties, and also gas barrier properties and mechanical strength, especially 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 includes 1) a tank for organic liquids, a pipe, a hot water pipe for floor heating, 2) a film requiring pinhole resistance, and 4) a film requiring stretchability and shrinkability. When used for a sheet, the performance is remarkably exhibited.

[0026] For fuel (gasoline etc.), agricultural chemicals, tanks and pipes of organic liquids such as organic liquids, conventionally, organic liquid permeability, 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.

Further, as a film application requiring pinhole resistance, a bag-in-box (BIB) or the like which uses a plastic film as an inner bag inside a cardboard box in response to recent resource saving. Applications are expanding. Therefore, since the composition of the present invention is imparted with flexibility, due to repeated bending due to vibration during transportation,
It is effective in improving the problem of pinholes and liquid leakage due to through holes.

On the other hand, examples of the film and sheet applications requiring stretchability 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.

[0030]

【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, ultra-low density polyethylene (B) (melt index = 1.3 g / 10 min, density = 0.89) 10 parts by weight, and further maleic anhydride modified polyethylene (C) (Mitsui After mixing 1 part by weight of Petrochemical Admer AT951), pelletization was performed 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 put into a single-layer film forming apparatus to obtain a film of 100 μ, and a JIS dumbbell No. 3 was used to add 10% tensile elongation to a gasoline at 40 ° C.
After immersion for a period of time and evaluation of stress cracking properties, no cracks were observed. In addition, the pellets were applied to a coextrusion multilayer direct blower of 5 layers of 3 types,
A multi-layer container was created. The composition of the sheet is such that both outermost layers have a high density (polyethylene resin layer) of 850μ, an adhesive resin layer (maleic anhydride-modified polyethylene) of 100μ, and the intermediate layer has the polyalcohol-based composition layer of 100μ.
Is. The obtained container was filled with gasoline, and the temperature was 40 ° C-6.
When left for 1 year under 5% RH condition, neither crack nor deterioration of gasoline barrier property was observed. As an accelerated test, the body of the container was cut off, and was subjected to 10% tensile elongation addition using JIS Dumbbell No. 3 as in the case of the above monolayer film, immersed in 40 ° C. gasoline for 3 hours, and evaluated for stress cracking property. However, no crack was observed. The gasoline permeability of the container is 0.01 g / m ² . da
It was y.

Example 2 Polyalcohol (B) obtained by reducing 90 parts by weight of polyalcohol (A) in Example 1 with 45 parts by weight of polyalcohol (A) and a polyketone composed of a carbon monoxide-ethylene copolymer. Repeating unit 90% represented by the formula (I), other 1
0%, intrinsic viscosity [η] = 1.2 dl / g} 45
A polyalcohol-based composition similar to that of Example 1 was applied to a 3-type 5-layer coextrusion device except that a blended product with parts by weight was used to form a multilayer sheet (polystyrene resin layer, adhesive resin layer / polyalcohol composition). Layer / adhesive resin layer / polystyrene resin layer). The composition of the sheet is 800 μm for both outermost polystyrene resin layers (Asahi Dow Styron 691) and an adhesive resin layer (Toso- “Mersen M-5”).
420 ", maleic acid-modified ethylene-vinyl acetate copolymer) is 50 μm each, and the intermediate layer (polyalcohol composition layer) is 50 μm. The sheet was subjected to a vacuum pressure air thermoforming machine (stretching rate 9 × 10% / min.) And molded at 130 ° C. As a result, the molded product was free from cracks, unevenness, uneven thickness, and had good appearance and transparency. When the humidity of this container was adjusted to 20 ° C.-65% RH and the oxygen transmission rate was measured (10/50 type, manufactured by Mocon), 0.9 cc. 20
μ / m ² . 24 hr. Not only does it show a very good gas barrier property with atm, but the variation in the measured values when 20 samples are measured (R = maximum oxygen permeability value-minimum oxygen permeability value) is very small at 0.3. It was a highly reliable container with high gas barrier properties.

Further, scraps and trims produced during thermoforming are crushed and subjected to a 4-type 7-layer coextrusion machine to obtain a multilayer sheet (polystyrene resin layer / collection layer / adhesive resin layer / polyalcohol composition layer / adhesive resin layer). / Collection layer / polystyrene resin layer) was prepared. The composition of the sheet is such that the outermost polystyrene resin layer 200 μ, the recovery layer 600 μ or the adhesive resin layer 100 μ, and the intermediate layer (polyalcohol composition layer)
Is 50 μ. The sheet moldability and thermoformability of the sheet were good, and the drop bag rupture strength of the container was not significantly different from that of the product not using the recovery layer.

Example 3 The polyalcohol composition used in Example 1 was applied to a three-kind five-layer coextrusion machine to obtain a multilayer film (polyethylene resin layer / adhesive resin layer / polyalcohol composition layer / adhesive resin layer /
A polyethylene resin layer) was prepared. The constitution of the multilayer film is such that the outermost polyethylene resin layer is 60 μm, the adhesive resin layer (Mitsui Petrochemical: Admer NF-500, maleic acid modified polyethylene) is 10 μm each, and the intermediate layer (EVOH composition layer). Is 10 μ. The obtained multilayer films were evaluated for flex resistance and adhesiveness by a Gelbo flex tester. As a result, a through hole (pinhole) was generated only after the number of flexing was 280, and the adhesive strength between the composition and Ad was 420 g / 15 mm width, which was a relatively good performance. This multilayer film was useful as an inner bag for a back-in-box.

Example 4 The carbon monoxide / ethylene / propylene molar ratio was 48/4.
8/4, polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene-propylene copolymer {96% of repeating units represented by the formula (I), and other 4
%, And mixed with 90 parts by weight of intrinsic viscosity [η] = 0.9 dl / g}, 10 parts by weight of ultra-low density polyethylene (B) (melt index = 1.3 g / 10 min, density = 0.89). Then, pelletization was performed under the conditions of Example 1. The same procedure as in Example 5 was carried out using the pellets. The resulting multilayer film started to have through holes (pinholes) after the number of flexing was 200, and the adhesive strength between the composition and Ad was 520 g.
/ 15 mm width and good performance was exhibited. This multilayer film was useful as an inner bag for a back-in-box.

Example 5 The polyalcohol composition used in Example 1 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 (Mitsui DuPont Chemical: 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. The film was conditioned at 20 ° C. and 100% RH, and the gas barrier property was measured (10/50 type, manufactured by Mocon Co.). Oxygen permeability 40 cc. 20 μ / m ² . 24 hr. Atm and good gas barrier property were exhibited. When the heat shrinkability at 70 ° C. was measured, the area shrinkage rate was 50%.

[0037]

The resin composition of the present invention has excellent mechanical properties such as bending resistance and pinhole resistance, and gas barrier properties,
Furthermore, it is excellent in stretch shrinkage and recoverability, and is also excellent in stress crack resistance against organic liquids such as gasoline.

Claims (5)

(57) [Claims] 1. A polyalcohol (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer, and a polyolefin (B), and a weight ratio of component (A) / component (B). The resin composition which is 99/1 to 1/99. 2. A maleic anhydride capable of reacting with a polyalcohol (A), a polyolefin (B) and (A) obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer.
In-acid group, epoxy group, silanol group, boronic acid group
It is composed of a modified polyolefin (C) having at least one functional group selected , and the component (A) / component (B) weight ratio is 99/1 to 1/99, and the component (C) / component {(A ) + (B)} in a weight ratio of 0.1 to 50/100. 3. The polyalcohol (A) is an alternating copolymer
The resin composition according to claim 1, which is a united body. 4. The tree according to any one of claims 1 to 3.
A multilayer structure comprising at least one layer of a fat composition. 5. The tree according to any one of claims 1 to 3.
A container comprising at least one layer of a fat composition.