JPH03124752A - Halogenated thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the moldability, appearance, strength properties, hydrophilicity, resistance to oil and solvent, gas barrier properties, etc., by compounding a specific halogenated thermoplastic resin with a melt-moldable vinyl alcohol-based polymer. CONSTITUTION:100-0.1wt.% vinyl chloride polymer-polyurethane hybrid compsn., contg. 10-90wt.% polyurethane and obtd. by reacting a polyol (e.g. a polyester polyol) impregnated into a powdered or particulate vinyl chloride polymer with a polyisocyanate (e.g. tetramethylene diisocyanate), is mixed with 0-99.9wt.% another halogenated polymer (e.g. a polyvinyl chloride) to give a halogenated thermoplastic resin. 100 pts.wt. said resin is compounded with 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).

Description

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

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, hoses, 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, hydrophilicity, 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 with hydrophilicity, oil resistance, solvent resistance, and gas barrier properties. - Although properties such as elasticity are improved, long-run molding is difficult because the two resins are hard to be compatible with each other in terms of wood quality, and the molded products obtained by melt molding tend to have foreign matter and coloring, and cannot be machined. There was also the problem that the physical properties of the material 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 improves various properties by blending a vinyl alcohol polymer into a halogen-containing thermoplastic resin, by using a specific co-reactive composition as at least a part of the halogen-containing thermoplastic resin. It attempts to solve problems.

Means for solving the problem, namely, the halogen-containing thermoplastic resin composition of the present invention,
Polyurethane content 1 obtained by reacting a polyol and a polyisocyanate in the coexistence of a vinyl chloride polymer
0 to 90% by weight of vinyl chloride polymer-polyurethane co-reaction composition (a1) 100 to 0.1% by weight and other halogen-containing polymers (a2) 0 to 99.88.8
To 100 parts by weight of a halogen-containing thermoplastic resin (A) consisting of % by weight, a melt-moldable vinyl alcohol polymer (B
)0.1 to 100 parts by weight.

The present invention will be explained in detail below.

Halogen-containing A The halogen-containing thermoplastic resin (A) is composed of the vinyl chloride polymer-polyurethane co-reaction composition (a1) alone, or the co-reaction composition (a1) and another halogen-containing polymer (a2). It consists of

<Co-reaction composition (at)> Vinyl chloride polymer-polyurethane co-reaction composition (a
1) is obtained by reacting a polyol and a polyisocyanate in the coexistence of a vinyl chloride polymer.

The reaction method is to add a polyol to a powdered or particulate vinyl chloride polymer to impregnate it, and then add polyisocyanate to produce polyurethane in the vinyl chloride polymer powder or particles. is preferably adopted. In addition, a method of producing polyurethane by mixing together a powdered or particulate vinyl chloride polymer, a polyol, and a polyisocyanate is also adopted.

The content of polyurethane in the resulting co-reactive composition is 1
It is necessary that the amount of the component be within the range of 0 to 90% by weight, and if the amount of the component is less than or greater than this range, the compatibility improving effect will be insufficient.

Here, as the vinyl chloride polymer, in addition to a homopolymer of vinyl chloride, a copolymer of vinyl chloride and one or more other comonomers is used. Other comonomers include vinyl acetate, ethylene, vinylidene chloride, and the like.

Among the urethane raw materials, polyols used include, for example, polyester polyols (condensed polyester polyols, lactone polyester polyols, polycarbonate diols, etc.), polyether polyols, and the like. Among these, condensed polyester polyols include adipic acid, succinic acid, azelaic acid, pimelic acid,
Dicarboxylic acids such as sebacic acid and phthalic acid or their lower alkyl esters and ethylene glycol, 1.4-
Butanediol, 1.6-hexanediol, 1.10
- Aliphatic diols without side chains such as decamethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,5-dimethyl-2,5-hexanediol.

Examples include those obtained by reacting with an aliphatic diol having a side chain such as 2.2-diethyl-1,3-propanediol and neopentyl glycol. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin-based polyalkylene ether glycol, and the like.

Among the urethane raw materials, polyisocyanates include, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexylmethane diisocyanate, 2.2.4- or 2,4.4-trimethylhexamethylene diisocyanate, Aliphatic or cycloaliphatic diisocyanates such as isopropylidene bis(4-cyclohexyl isocyanate), methylcyclohexane diisocyanate, inphorone diisocyanate,
2.4- or 2.6-) lylene diincyanate, diphenylmethane-4゜4''-diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate,
m- or p-7 enylene 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.

<Other halogen-containing polymers (a2)> Halogen-containing polymers other than the co-reaction composition (a1) (
Examples of a2) include vinyl chloride polymers, vinylidene chloride polymers, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-vinyl acetate copolymers, and chlorosulfonated polyethylene. 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 (acetalized products, ketalized products, cyanoetherified products, etc.), seven polymers copolymerizable with vinyl acetate (e.g., olefins such as ethylene, propylene, isobutyne, α-octene, α-octadecene, unsaturated Comonomers such as carboxylic acids or their salts, partial alkyl esters, complete alkyl esters, nitriles, amides, anhydrides, unsaturated sulfonic acids or their salts, and vinyl esters other than vinyl acetate) and vinyl acetate. Chemicals are used. However, the copolymerization ratio of the monomer copolymerizable with vinyl acetate is required to be 75 mol % or less in the case of ethylene, and 30 mol % or less in the case of heptamers 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 CB), preferred are low ash and low alkali metal vinyl alcohol polymers whose melting temperature is 200° C. or less, and which 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 an acetate of the alkali metal 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, 5000 to s o o o o pp.
m, the alkali metal content is, for example, 4000 to 400
It is about 00pp■.

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 completely iodizing 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.
This is the value obtained by leaving it for a minute and depositing the ash.

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 300
ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less, and the alkali metal content is 2
It is particularly preferable to use a saponified ethylene-vinyl acetate copolymer with a low ash content and a low alkali metal content of 00 ppm or less, preferably 35 ppm or less, more preferably 5 ppm 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 set when the ash content is i p
pm, and the alkali metal content is about 0.5 pp.

In order to obtain the above-mentioned vinyl alcohol-based polymer having a low ash content and a low alkali metal content, powder of the polymer is used.

Particles and pellets are thoroughly washed with an acid, especially a solution of a weak acid in water or an organic solvent such as methanol, to remove salts that cause ash and alkali metals, and then preferably washed with water or an organic solvent such as methanol. The method used is to remove the acid attached to the resin and dry it. 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, azelaic acid, geltaric acid,
Succinic acid, benzoic acid, isophthalic acid, terephthalic acid, etc. are used. Normally, pKa at 25°C is 3.5
The above are useful.

In addition, after the above-mentioned treatment with a weak acid, a dilute strong acid such as an organic acid with a pKa of 2.5 or less at 25°C such as oxalic acid or maleic acid, or phosphorous acid may be used before or after washing with water or an organic solvent such as methanol. 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.

The proportion of the vinyl chloride polymer-polyurethane co-reaction composition (a1) in the halogen-containing thermoplastic resin (A) is 0
．． The proportion of the co-reaction composition (a1) should be 0.1% by weight to 100% by weight, and the remainder should be a halogen-containing polymer (a2) other than the above, such as a normal vinyl chloride polymer. If it is less than 1% by weight, compatibility with the vinyl alcohol polymer (B) will be insufficient, and moldability, appearance and physical properties of the molded product will be impaired.

The blending ratio of the vinyl alcohol polymer (B) to 100 parts by weight of the halogen-containing thermoplastic resin (A) consisting of the above-mentioned co-reaction composition (a1) or this and another halogen-containing polymer (a2) is 0. .1 to 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).

1. In addition to the above-mentioned components, the present invention also includes, if necessary, plasticizers, antioxidants, stabilizers, stabilizing aids, ultraviolet absorbers, dyes and pigments, fillers, lubricants, antistatic agents, surfactant,
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.

11-order vinyl chloride polymer-thermoplastic polyurethane co-reaction composition (a1), other halogen-containing polymers (a2)
, the vinyl alcohol polymer (B), and other additives are mixed simultaneously or in any order and subjected to melt molding.

Symptoms I Melt molding methods include 5 calendar molding methods, extrusion molding methods,
Injection molding method, blow molding method, etc. can be adopted.

In the present invention, when melt-molding a blend of a halogen-containing thermoplastic resin (A) and a vinyl alcohol polymer (B), as at least a part of the halogen-containing thermoplastic resin (A), Since the specific vinyl chloride polymer-polyurethane co-reaction composition (a1) is used, the lack of compatibility between the vinyl alcohol polymer CB) and the halogen-containing thermoplastic resin (A) is effectively improved, and its moldability is improved. And the effect of improving the physical properties of the halogen-containing thermoplastic resin (A) by the vinyl alcohol polymer (B) is 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) and a vinyl alcohol polymer (B).

Halogen A coexistence reaction composition (a1) > (al-t) Polyvinyl chloride with a degree of polymerization of 1100, which was mixed in advance with 1 part by weight of calcium stearate and 1 part by weight of zinc stearate and stirred at high speed for 2 minutes in a Henschel mixer. Add 140 parts by weight of a polyester polyol with a molecular weight of 2000 obtained by condensation of adipic acid and 1,4-butanediol/neopentyl glycol (molar ratio 9/1) to 100 parts by weight of powder while heating to 70°C. 10
After stirring and mixing at 0°C for 10 minutes, 9 parts by weight of tolylene diisocyanate was added, the temperature was raised to 110°C, and stirring and mixing was continued for 1 hour to perform a urethanization reaction.

The reaction mixture was cooled to room temperature and powdered polyvinyl chloride was added.
A polyurethane co-reactive composition was obtained. The polyurethane content was 52%.

(al-2) 100 parts by weight of polyvinyl chloride powder with a degree of polymerization of 1100, 1 part by weight of calcium stearate, 1 part by weight of zinc stearate, adipic acid and 1,4-butanediol/neopentyl glycol (molar ratio 9/1) The above (al-
A powdered polyvinyl chloride-polyurethane co-reaction composition was obtained according to 1). The polyurethane content was 30%.

(at-3) 100 parts by weight of polyvinyl chloride powder with a degree of polymerization of 1100, 1 part by weight of calcium stearate, 1 part by weight of zinc stearate, and a polyester with a molecular weight of 2000 obtained by condensation of sebacic acid and 1,6-hexanediol. A powdered polyvinyl chloride-polyurethane co-reaction composition was obtained according to (al-1) above using 140 parts by weight of polyol and 12 parts by weight of tolylene diisocyanate. The polyurethane content was 60%.

<Halogen-containing polymer (a1) other than the above> (al-1
) Polyvinyl chloride (al-2) with a degree of polymerization of 800 Vinyl chloride 1-nodene-methyl acrylate copolymer vinyl alcohol system with a methyl acrylate content of 7 mol% B (B-1) Ethylene content of 44 mol%, vinyl acetate moiety saponification degree of 9
Saponified ethylene-vinyl acetate copolymer (B-2) with 9.5 mol%, melting point 167°C, ash content 6 ppm, and sodium metal content 2.7 pp.Ethylene content 55 mol%, saponification degree of vinyl acetate portion 7
8.0 mol%, melting point 111°C. Saponified ethylene-vinyl acetate copolymer (B-3) with ash content of 15 ppm, sodium metal content of 4.0 ppm, dodecene-1 content of 5.5 mol%, saponification degree of vinyl acetate portion of 9883 mol%, melting point of 187°C, ash content 215pp■
, Sodium metal content 14 Opp Dodecene-1/vinyl acetate copolymer saponified product (B-4) Degree of polymerization 500, degree of saponification 70.0 mol%, melting point 170°C
, ash content 120 ppm, sodium metal content 709 PII
Polyvinyl alcohol - Blend composition, molding conditions - After premixing the above materials in the proportions shown in Table 1, extrusion molding was performed under the following conditions. Hereinafter referred to as “Department”
The numbers are parts by weight.

When the halogen-containing polymer (a1) was polyvinyl chloride, the formulation and extrusion molding conditions were set as follows.

<Combination prescription> Co-reaction composition (a1) Description polyvinyl chloride (a1) Description ((a1) and (a
The total amount of 1) is 100 parts) vinyl alcohol polymer (
B) Description: Epoxidized soybean oil 3
Part Calcium stearate 0.5 parts Zinc stearate 0.5 parts Stearoylbenzoylmethane 0.2 parts (Extrusion molding conditions) Extruder: 30mm diameter extruder T die: 200mm width, sheet thickness 0.3mm Screw: Full flight constant Pitch, L/D = 20, compression ratio 3.0, rotation speed 3 Orpm Temperature: C1130℃, C2175℃, C318
0°C, H170°C, D 180°C Screen = 80 mesh x 2 take-up roll 285-90°C Also, the compounding recipe and extrusion when the halogen-containing polymer (a2) is vinylidene chloride-methyl acrylate copolymer The molding conditions were set as follows.

Blending prescription> Co-reaction composition (a1) Notation Vinylidene chloride-methyl acrylate copolymer (a2)
Notation (Total amount of (at) and (a2) is 100 parts) Vinyl alcohol polymer Epoxidized soybean oil Calcium stearate Zinc stearate Stearoyl benzoyl Methane (Extrusion molding conditions) D = 23, compression ratio 3.2, rotation speed 3 Orpm (other conditions are the same as the extrusion molding conditions described above) (B)
Description 3 parts 0.5 parts 0.5 parts Tan 0.2 parts The 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 square thick 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,
,〉70,)81. >56J means 10 tests
It shows that the minimum values in the case of are 74.70.81°56, respectively.

Discharge half-life was measured using an honest meter. In addition, in the case of the halogen-containing thermoplastic resin (A) alone, the resin (A) is (al-1) (al-2) (at-3)
, (a2-1), and (a2-2), or even if they are used together in any ratio, the discharge half-life will be ■.

Claims (1)

[Scope of Claims] 1. Vinyl chloride polymer-polyurethane co-reaction composition (a1 ) 100 to 0.1% by weight and 100 parts by weight of a halogen-containing thermoplastic resin (A) consisting of 0 to 99.9% by weight of other halogen-containing polymers (a2), a vinyl alcohol polymer that can be melt-molded. (B)0
．． A halogen-containing thermoplastic resin composition containing 1 to 100 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.