JPH03124751A - Halogen-containing thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the moldability, appearance, strength properties, hydrophilicity, resistance to oil and solvent, and gas barrier properties by compounding a halogenated thermoplastic resin, a melt-moldable vinyl alcohol- based polymer, and a thermoplastic polyurethane resin. CONSTITUTION:The title compsn. comprises 100 pts.wt. halogenated thermoplastic resin (e.g. polyvinyl chloride); 0.1-100 pts.wt. melt moldable, low ash and low alkali metal vinyl alcohol-based copolymer having an m.p. of 200 deg.C or lower, an ash content of 300ppm or lower, and an alkali metal content of 200ppm or lower (e.g. a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20-75mol% and a saponification degree of vinyl acetate part of 50mol% or higher); and 0.1-300 pts.wt. thermoplastic polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a halogen-containing thermoplastic resin composition that has good properties such as processability, appearance, strength, hydrophilicity, oil and solvent resistance, and gas barrier properties. It is something.

Conventional technology Vinyl chloride polymers are relatively inexpensive resins and have excellent properties such as transparency, mechanical properties, and processability.
It is used in a wide range of applications, including films, sheets, poses, flexible containers, canvas, leather, tarpaulins, shoe soles, sponges, wire coverings, and daily necessities.

Although vinyl chloride polymers are resins having the above-mentioned advantages, they have disadvantages such as poor processability, wood affinity, oil and solvent resistance, gas barrier properties, and adhesion to substrates.

Therefore, in order to improve the processability, wood affinity, and other properties of vinyl chloride-based polymers, polymer blending of modifying resins with vinyl chloride-based polymers has been carried out. - Blending a saponified vinyl acetate copolymer is being practiced.

For example, JP-A-52-69955 discloses a vinyl chloride polymer barrier packaging composition made of a mixture of a vinyl chloride polymer and 10 to 30% by weight of an ethylene/vinyl alcohol copolymer. has been done.

JP-A-60-238345 discloses: ■ thermoplastic resins (including vinyl chloride polymers), ■ saponified ethylene-vinyl acetate copolymers, and ■ selected from Groups 1, 2, and 3 of the periodic table. Resin compositions comprising salts or oxides containing at least one element are disclosed, and these compositions are described as having significantly improved compatibility.

Note that Japanese Patent Publication No. 59-39464 discloses a vinyl chloride polymer-polyurethane alloy obtained by reacting a polyol and a polyisocyanate in the coexistence of a vinyl chloride polymer. However, no consideration is given to combining this co-reactive polymer alloy with a vinyl alcohol polymer.

Problems to be Solved by the Invention However, the method of blending a saponified ethylene-vinyl acetate copolymer with a halogen-containing thermoplastic resin such as a vinyl chloride polymer has problems such as wood affinity, oil resistance, solvent resistance, Although properties such as gas barrier properties are improved, long-run molding is difficult because the two resins are woody and difficult to be compatible with each other, and foreign matter and coloring are observed in molded products obtained by melt molding. There was a problem in that mechanical properties also deteriorated.

In this regard, although the composition described in JP-A No. 60-238345 has an improvement effect in terms of compatibility, there is a natural limit to the improvement of compatibility by adding salts and oxides, and there is a limit to practical use. There is still room for improvement from this perspective.

The present invention attempts to solve the above-mentioned conventional problems by blending a vinyl alcohol polymer into a halogen-containing thermoplastic resin to improve various properties, and further blending a thermoplastic polyurethane resin. .

Means for solving the problem, namely, the halogen-containing thermoplastic resin composition of the present invention,
100 parts by weight of halogen-containing thermoplastic resin (A), 0.1 to 10 parts by weight of melt-mouldable vinyl alcohol polymer (B)
0 parts by weight and thermoplastic polyurethane resin (C) 0.1
~300 parts by weight.

The present invention will be explained in detail below.

Halogen A Examples of the halogen-containing thermoplastic resin (A) include vinyl chloride polymers, vinylidene chloride polymers, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-vinyl acetate copolymers, and chlorosulfonated polyethylene. It will be done. Particularly important are vinyl chloride-based polymers, that is, homopolymers of vinyl chloride or copolymers of vinyl chloride and other comonomers.

Vinyl alcohol B) As the vinyl alcohol polymer (B), melt-moldable vinyl alcohol homopolymers or copolymers, such as polyvinyl alcohol with a relatively low degree of polymerization, partially saponified polyvinyl acetate, polyvinyl alcohol Post-modified products of alcohol (acetals, ketals, cyan ethers, etc.), monomers copolymerizable with vinyl acetate (for example, olefins such as ethylene, propylene, isobutyne, α-octene, α-octadecene, unsaturated carboxylic acids, etc.) or its salts, partial alkyl esters, complete alkyl esters, φ nitriles, φ amides, anhydrides, unsaturated sulfonic acids or their salts, comonomers such as vinyl esters other than vinyl acetate) saponified products of copolymers with vinyl toacetate, etc. used. However, it is required that the copolymerization ratio of the monomer copolymerizable with vinyl acetate is 75 mol % or less in the case of ethylene, and 30 mole % or less in the case of 7 monomers other than ethylene.

Among these, ethylene-vinyl acetate copolymers with an ethylene content of 20 to 75 mol% (preferably 25 to 60 mol%) and a degree of saponification of the vinyl acetate moiety of 50 mol% or more (preferably 70 mol% or more) are preferred. halogen-containing thermoplastic resins (A) are the most important, and those whose copolymerization composition deviates from the above range lack the effect of improving the properties of the halogen-containing thermoplastic resin (A). Note that as long as the copolymer composition has the above copolymerization composition, it may also contain a small amount of other comonomers.

Among the above-mentioned vinyl alcohol polymers (B), preferred are low ash and low alkali metal vinyl alcohol polymers whose melting temperature is 200°C or less and have an ash content and alkali metal content of -quantity or less. .

Halogen-containing thermoplastic resins are generally molded at a temperature of 200°C or lower, so if the melting temperature exceeds 200°C, the vinyl alcohol polymer will not be completely melted and miscible dispersion will be incomplete. Desired physical properties cannot be obtained as a molded product of the composition.

Furthermore, if the ash content and alkali metal content exceed a predetermined amount, the halogen-containing thermoplastic resin is likely to be colored or decomposed during molding.

Generally, a saponified vinyl acetate copolymer is produced by saponifying a vinyl acetate copolymer with an alkali catalyst. However, the industrial water and reagents used contain metal salts as impurities, and the saponification catalyst (alkali metal hydroxide) remains as alkali metal acetate even after the reaction. Therefore, these impurities and alkali metal acetate are precipitated from the saponification liquid and are contained in the resin filtered out. Although it cannot be said unconditionally, it depends on various factors such as the copolymerization component content of the resin, the degree of saponification, and the saponification conditions.
Usually, the ash content in the saponified vinyl acetate copolymer obtained above is, for example, about 5,000 to 50,000 ppm,
The alkali metal content is, for example, 4000 to 40000 pp.
It is about m.

Also, in the production of polyvinyl alcohol or its subsequent modified products, acids or alkalis are used as catalysts, and when acids are used as catalysts, metal hydroxides or carbonates are used in the neutralization step after the reaction. It will contain a considerable amount of alkali metals.

Here, the ash content refers to dry saponified vinyl acetate copolymer taken in a platinum evaporating dish, carbonized using an electric heater and gas burner, placed in an electric furnace at 400°C, heated to 700°C,
After being completely incinerated at 700℃ for 3 hours, it was taken out from the electric furnace, left to cool for 5 minutes, and placed in a desiccator for 25 minutes.
The ash content is determined by leaving it for a minute and then measuring the ash content.

Alkali metals are determined by atomic absorption spectrometry using a solution in which the saponified vinyl acetate copolymer is incinerated in the same manner as in the case of ash measurement, and the ash is dissolved in an acidic aqueous solution of hydrochloric acid under heating.

In the present invention, the ash content defined above is 30O
ppm or less, preferably 50ppm or less, more preferably 20pp or less, and the alkali metal content is 20ppm or less.
It is particularly preferable to use a saponified ethylene-vinyl acetate copolymer with a low ash content and a low alkali metal content of 0 ppm or less, preferably 35 PPII or less, and more preferably 5 PPII or less.The ash content and alkali metal content are within the above ranges. However, from an industrial standpoint, there is a limit to refining, so the lower limit is when the ash content is 1.
ppm, and the alkali metal content is about 0.5 ppm.

To obtain the above-mentioned low ash-low alkali metal content vinyl alcohol-based polymer, the powder, particles, or pellets of the polymer are thoroughly washed with an acid, especially a weak acid solution in water or an organic solvent such as methanol, to reduce the ash content. After removing salts that cause alkali metals and alkali metals, a method of washing the resin with an organic solvent such as water or methanol to remove acid adhering to the resin, and then drying the resin is used. Note that the water used for preparing the aqueous solution, washing, etc. mentioned above or below is deionized water.

Examples of weak acids include acetic acid, propionic acid, glycolic acid, lactic acid, adipic acid, and azelaic acid.

Geltaric acid, succinic acid, benzoic acid, isophthalic acid, terephthalic acid, etc. are used. Normally, p at 25°C
Those having a Ka of 3.5 or more are useful.

In addition, after the treatment with the above-mentioned weak acid, and before or after washing with water or an organic solvent such as methanol, dilute strong acids, such as organic acids with a pKa of 2.5 or less at 25°C such as oxalic acid and maleic acid, or phosphorus It is desirable to further treat with an aqueous solution such as acid, sulfuric acid, nitric acid, hydrochloric acid, etc., which makes the alkali metal removal more efficient.

Saku Polyurethane C Thermoplastic polyurethane resin (C) is obtained by reacting the following polyol and polyisocyanate.

Among the urethane raw materials, polyols used include, for example, polyester polyols (condensed polyester polyols, lactone polyester polyols, polycarbonate polyols, etc.), polyether polyols, and the like.

Among these, condensation polyester polyols include dicarboxylic acids such as adipic acid, succinic acid, azelaic acid, pimelic acid, sebacic acid, and phthalic acid, or lower alkyl esters thereof, ethylene glycol, 1,4-butanediol, l, 6 -Aliphatic diols without side chains such as hexanediol, 1,10-decamethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,5-dimethyl-2,5-hexanediol, 2 Examples include those made by reacting with an aliphatic diol having a side chain such as 2-diethyl-1,3-propanediol and neopentyl glycol.

Examples of lactone polyester polyols include β-propiolactone, pivalolactone, δ-valerolactone,
(-caprolactone, methyl-ε-caprolactone, dimethyl-(-caprolactone, trimethyl-ε-caprolactone, and other lactone compounds) are reacted with hydroxy compounds such as short-chain polyols.

As the polycarbonate polyol, those obtained by transesterification of a hydroxy compound such as a short chain polyol and diallyl carbonate, dialkyl carbonate or ethylene carbonate are used.

For example, poly-16-hexamethylene carbonate,
Poly-2,2'-bis(4-hydroxyhexyl)propane carbonate and the like are industrially produced and easily available.Another method for obtaining polycarbonate polyols is by the so-called phosgene method (or solvent method). I can do it.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxypropylene glycol, and glycerin-based polyalkylene ether glycol.

In addition to the above, various known polyols for polyurethane can also be used.

Note that when comparing polyester polyols and polyether polyols, the former is more important.

Examples of polyisocyanates among urethane raw materials include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexylmethane diisocyanate, and 2.2.4- or 2,4.4-) dimethylhexamethylene diisocyanate. , aliphatic or cycloaliphatic diisocyanates such as inpropylidene bis(4-cyclohexyl isocyanate), methylcyclohexane diisocyanate, inphorone diisocyanate,
2,4- or 2,6-) lylene diisocyanate, diphenylmethane-4°4'-diisocyanate, 3-methyldiphenylmethane-4,4'-diincyanate,
m- or p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1
, 5-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 7 ducts of polyhydric alcohol and polyisocyanate, etc. are used.

In the urethanization reaction, chain extenders such as polyhydric alcohols and polyhydric amines can also be used.

The blending ratio of the vinyl alcohol polymer CB) to 100 parts by weight of the Arrangement 1 alloy halogen thermoplastic resin (A) is 0.1 to 1.
selected from a range of 100 parts by weight. A more preferable range is 0.5 to 50 parts by weight. Too little of the vinyl alcohol polymer (B) lacks the effect of improving the properties of the halogen-containing thermoplastic resin (A), and too much of it impairs the original properties of the halogen-containing thermoplastic resin (A).

In addition, the blending ratio of the thermoplastic polyurethane resin (C) to 100 parts by weight of the halogen-containing thermoplastic resin (A) is 0.
．． It is selected from the range of 1 to 300 parts by weight. A more preferable range is 5 to 150 parts by weight. Too little thermoplastic polyurethane resin (C) means that the halogen-containing thermoplastic resin (A
) is insufficient in compatibility with the vinyl alcohol polymer (B), resulting in poor moldability, appearance and physical properties of the molded product. On the other hand, excessive amount of thermoplastic polyurethane resin (C)
The original properties of the halogen-containing thermoplastic resin (A) are impaired.

1 In the present invention, in addition to the above-mentioned components, if necessary, plasticizers, antioxidants, stabilizers, stabilizing aids, ultraviolet absorbers, dyes and pigments, fillers, lubricants, antistatic agents, and interfaces are used. activator,
Known additives for polyvinyl chloride resins such as chelating agents, reinforcing agents, blowing agents, flame retardants, and impact resistance improvers can be blended. Furthermore, other thermoplastic resins may be blended as long as they do not impair the spirit of the present invention.

The halogen-containing thermoplastic resin (A), the vinyl alcohol polymer (B), the thermoplastic polyurethane resin (C), and other additives are mixed simultaneously or in any order and melt-molded. Served.

Disease 1ULl Melt molding methods include calendar molding method, extrusion molding method,
Injection molding method, blow molding method, etc. can be adopted.

Effects of the Invention In the present invention, since a thermoplastic polyurethane resin (C) was used in combination with the melt molding of the blend of the halogen-containing thermoplastic resin (A) and the vinyl alcohol polymer (B), the vinyl alcohol polymer The lack of compatibility between the polymer (B) and the halogen-containing thermoplastic resin (A) is effectively improved,
The moldability and the effect of improving the physical properties of the halogen-containing thermoplastic resin (A) by the vinyl alcohol polymer (B) are significantly improved.

Therefore, plate-out is not observed in the case of calendar molding, and long-run molding is possible in the case of extrusion molding, and the coloring of the resulting molded product is effectively suppressed, and the appearance and physical properties are also favorable. .

Example Next, the composition of the present invention will be further explained with reference to Examples.

Preparation of one material - The following were prepared as a halogen-containing thermoplastic resin (A), a vinyl alcohol polymer (B), and a thermoplastic polyurethane resin (C).

Halogen A (A-1) Polyvinyl chloride with a degree of polymerization of 1100 (A-2) Vinylidene chloride-methyl methacrylate copolymer vinyl alcohol with a methyl methacrylate content of 7 mol% B (B-1) Ethylene content of 44 mol%, Saponification degree of vinyl acetate part: 8
Saponified ethylene-vinyl acetate copolymer (B-2) with 3.5 mol%, melting point 167°C, ash content 6PP layer, sodium metal content 2.7pp hazy Ethylene content 55 mol%, degree of saponification of vinyl acetate portion 7
9.0 mol%, melting point 111°C, ash 15 ppm, sodium metal content 4. Saponified ethylene-vinyl acetate copolymer of Opp oil (B-3) Dodecene-1 content 5.5 mol%, degree of saponification of vinyl acetate portion 88.3 mol%, melting point 187°C, ash content 215pp layer, sodium metal Saponified dodecene-1/vinyl acetate copolymer with a content of 140 ppm (B-0, degree of polymerization 500, degree of saponification 70.0 mol%, melting point 170°C
, ash content 120PP■, sodium metal content';ropp
Polyvinyl alcohol polyurethane C (C-1) Polyester polyol with a molecular weight of 2000 obtained by condensation of adipic acid and 1,4-butanediol/neopentyl glycol (mole ratio 9/l), tolylene diisocyanate and Thermoplastic polyurethane obtained by reacting (C-2) Commercially available thermoplastic polyurethane ("Pandex T-5000PJ" manufactured by Dainippon Ink and Chemicals Co., Ltd., urethane type is polyester) (C-3) Thermoplastic polyurethane (“Vandex T-6085” manufactured by Dainippon Ink and Chemicals Co., Ltd., urethane type is polyether type) - Composition, molding conditions - Using each of the above materials in the proportions shown in Table 1 After premixing, extrusion molding was performed under the following conditions. Hereinafter, "parts" refer to parts by weight.

When the halogen-containing thermoplastic resin (A) was (A-1), the formulation and extrusion molding conditions were set as follows.

<Blending prescription) Polyvinyl chloride (A-1) 100 parts vinyl alcohol polymer CB) Description Thermoplastic polyurethane resin (C) Description Stabilizer
8.5 parts The composition of the stabilizer was as follows.

<Extrusion molding conditions> Extruder: 30 layer diameter extruder T die: 200mm width, sheet thickness 0.3m
m screw: full flight constant pitch, L/D = 20, compression ratio 3.0, rotation speed 30rp Layer temperature: C1150℃, 02175℃, 0318
5°C, H170°C, D 185°C Screen 280 mesh x 2 take-up rolls = 85-90°C When the halogen-containing thermoplastic resin (A) is (A-2), the compounding recipe and extrusion molding conditions are as follows. I set it like this.

<Blending prescription) Vinylidene chloride-methyl methacrylate copolymer (A-2) Zoo part bivinyl alcohol polymer) Description thermoplastic polyurethane resin (C) Description stabilizer
4.2 parts The composition of the stabilizer was as follows.

<Extrusion molding conditions) Extruder: 40cm diameter extruder screw: L/D = 23, compression ratio 3.2, rotation speed 3O
rpm (Other conditions are the same as the extrusion molding conditions described above) Conditions and results are shown in Table 1.

Note that the measurements and evaluations were performed as follows.

Extrusion moldability is the drawdown during continuous molding for 8 hours,
Judgment was made based on the presence or absence of abnormalities such as torque changes.

The appearance of the molded product was evaluated based on the presence or absence of coloring, fish eyes, vertical stripes, etc. after continuous molding for 8 hours.

The total light transmittance was measured according to JIS K8745 (1 layer thickness sheet).

Impact strength is Izotsu impact strength according to JIS K7110.
"Non-destructive" in the table indicates that it is non-destructive in all 10 tests,
, >50. >55, >60” means the number of tests
It shows that the minimum values in the case of are 45.50.55.60, respectively.

Discharge half-life was measured using an honest meter. In addition, in the case of the halogen-containing thermoplastic resin (A) alone, (A
-1) and (A-2), the discharge half-life is ■.

Claims (1)

[Claims] 1. 100 parts by weight of the halogen-containing thermoplastic resin (A) and 0.1 to 0.1 to 100 parts by weight of the melt-moldable vinyl alcohol polymer (B).
100 parts by weight and thermoplastic polyurethane resin (C) 0
．． A halogen-containing thermoplastic resin composition containing 1 to 300 parts by weight. 2. The vinyl alcohol polymer (B) has a melting temperature of 20
The composition according to claim 1, which is a low ash/low alkali metal vinyl alcohol polymer having a temperature of 0° C. or lower, an ash content of 300 ppm or less, and an alkali metal content of 200 ppm or less. 3. The composition according to claim 1, wherein the vinyl alcohol polymer (B) is a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 75 mol% and a degree of saponification of the vinyl acetate portion of 50 mol% or more. . 4. A saponified ethylene-vinyl acetate copolymer with an ethylene content of 20 to 75 mol% and a degree of saponification of the vinyl acetate portion of 50 mol% or more, a melting temperature of 200°C or less, and an ash content of 300
4. The composition according to claim 3, which is a saponified ethylene-vinyl acetate copolymer having a low ash content and a low alkali metal content of 200 ppm or less.