WO1999005211A1

WO1999005211A1 - Vinylidene fluoride resin compositions and articles molded therefrom

Info

Publication number: WO1999005211A1
Application number: PCT/JP1997/002596
Authority: WO
Inventors: Seiichi Ohira; Kazuyuki Munakata; Toshiya Mizuno; Nobuyuki Masumura
Original assignee: Kureha Chemical Industry Co., Ltd.
Priority date: 1996-01-31
Filing date: 1997-07-28
Publication date: 1999-02-04
Also published as: JPH09208783A

Abstract

A vinylidene fluoride resin composition which is so thermally stable as not to cause blowing or discoloration even at the processing temperature; and articles molded from the composition. The resin composition comprises 100 parts by weight of a vinylidene fluoride resin and 0.01 to 0.5 part by weight of a phosphite compound. The composition may further contain a phenol compound.

Description

Vinylidene fluoride resin composition and molded article

Technical field

The present invention relates to a thermally stable vinylidene fluoride resin composition. For more information,

A specific amount of phosphite compound is blended with vinylidene fluoride-based resin.

The present invention relates to a vinylidene fluoride resin composition that can be formed without foaming or coloring. The present invention also relates to a molded product formed from the composition.

Background art

Vinylidene fluoride resin is a thermoplastic resin that has good mechanical properties and is excellent in weather resistance, chemical resistance, and abrasion resistance, and is formed into various molded products. The vinylidene fluoride resin is molded at a molding temperature of 200 to 350 ° C by operations such as compression molding, injection molding, extrusion molding, and blow molding. At such a molding temperature, the vinylidene fluoride resin is thermally degraded.Therefore, like other plastics, additives such as antioxidants are used to ensure the stability during processing. Can be For example, Japanese Patent Publication No. 53-44953 discloses that a vinylidene fluoride resin and an organic phosphite of a polyhydric alcohol and a penter, a dipenter and a tripentaerythritol are used. Disclosed are compositions of a stabilizer and vinylidene fluoride resin, alone or in combination with a mixture. In the invention of this publication, when used as a coating composition, the deterioration time and adhesion time of the organic phosphite alone of polyhydric alcohol added to the fusibinylidene resin are hardly improved. Deterioration time by adding 0.5 to 5% by weight of an organic phosphite of a polyhydric alcohol in the presence of 0.1 to 2% by weight of a polyhydric alcohol such as penter, dipenter, and tripentaerythritol, An improvement in the adhesion time has been observed. In addition, in observing the coloring state of the sheet molded under pressure on a heat press kept at 230 ° C, The effect is recognized when the organic phosphite of the polyhydric alcohol is 0.5% by weight or more based on the vinylidene fluoride resin and the amount is equal to or more than that of the phenol erythritol added at the same time. It is also described that in this case as well, when only 2% by weight of an organic phosphite of a polyhydric alcohol is added, coloring occurs.

In addition, a phenolic antioxidant is generally used as an antioxidant for improving the heat-resistant life during molding of a thermoplastic resin. However, when the processing temperature is 200 ° C or more and the processing is affected by strong shearing force, the synergistic effect can be seen by using a phenol-based antioxidant in combination with a phosphorus-based antioxidant. It has been recognized that the ratio of phosphorus antioxidant / phenol based on a large amount of phosphorus antioxidant = 3Z1 to 1Z1 is effective. Chemical Industry, April 19, 1917 (pp. 17-19).

Also, Japanese Patent Application Laid-Open No. H 1-25256769 discloses that a composition obtained by adding a specific cyclic phosphate compound and a phenol compound to various thermoplastic resins improves the thermal stability of the thermoplastic resin. However, in the case of adding both, the specific addition ratios of these compounds are such that the amount of the phenol compound added is the same as or smaller than that of the cyclic phosphite compound.

As described above, various compositions for forming a thermoplastic resin are known, but a vinylidene fluoride resin composition capable of sufficiently suppressing a foaming phenomenon and coloring at a processing temperature is not known.

In view of such circumstances, the present inventors have conducted intensive studies. As a result, in the above-mentioned known documents, even when 2% by weight of a phosphite compound was added to vinylidene fluoride resin in the presence of pentaerythritol, the coloring was performed. However, surprisingly, when a small amount of the phosphite compound alone is added, that is, 0.01 to 0.5 parts by weight of the phosphite compound is added to 100 parts by weight of the vinylidene fluoride resin. The fusibinylidene-based resin composition obtained by mixing has heat resistance at a processing temperature of 280 ° C or higher, and suppresses thermal deterioration.As a result, a molded product without coloring can be obtained without causing a foaming phenomenon. And that a specific amount of a phenol compound is allowed to coexist in this composition. Thus, the present inventors have found that there is an effect of preventing the foaming phenomenon and coloring even at a high temperature, and reached the present invention.

That is, an object of the present invention is to provide a stable vinylidene fluoride resin composition which does not cause a foaming phenomenon or coloring at a processing temperature. Disclosure of the invention

In the present invention, 1 0 0 parts by weight of vinylidene fluoride resin and Hosufai DOO compound 0. 0 1 ~ 0. 5 _c The above composition characterized in that it is a vinylidene fluoride resin composition comprising by weight parts, This is a vinylidene fluoride resin composition to which a phenol compound is added in an amount of 0 to 10 times the weight of a phosphite compound. Further, it is a molded product obtained from these compositions.

A preferred embodiment is a vinylidene fluoride resin composition comprising a phenol compound in an amount of 2 to 6 times the phosphite compound in the above composition, and is obtained from these compositions. It is a molded product. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, a vinylidene fluoride resin is a vinylidene fluoride homopolymer, a copolymer physically and chemically similar to the homopolymer, and containing 70% by mole or more of vinylidene fluoride as a structural unit. And a mixture of these polymers. Monomers that copolymerize with vinylidene fluoride include tetrafluoroethylene, propylene hexafluoride, ethylene trifluoride, ethylene trifluoride, vinyl fluoride, and the like.One or more of these may be used. Can be used. The phosphite compound used in the present invention includes a polyhydric alcohol having 3 to 5 carbon atoms such as pentaerythritol and propanetriol or an oligomer thereof having 1 to 3 phosphorus atoms (trivalent) formed through an ester bond. A phosphite compound obtained by transesterification of one to three phosphite esters represented by P≡ (0-alkyl or phenyl) ₃ with the polyhydric alcohol described above. preferable. Specifically, bis (2,6-di-tert-butyl-14-methylphenyl) -pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, Stearyl pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, tetra (diphenylphosphite) pentaerythritol, diphenylpentaerythritol diphosphite, triphenyldipentaerythritol phosphite, Examples thereof include tripentaerythritol diphosphite, phenylneopentyl phosphite, and trimethylolpropane phosphite. Also, tri (alkyl-substituted or unsubstituted phenyl) phosphites such as tris (nonylphenyl) phosphite, trialkyl phosphites such as tris (2-ethylhexyl) phosphite and tris (tridecyl) phosphite And diphenylmono (2-ethylhexyl) phosphite can also be used.

The phenolic compound used in the present invention is preferably a compound having 1 to 4 benzene rings substituted with 1 to 3 alkyl groups and hydroxy groups in a molecule and having a phenolic OH group. More specifically, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-14-hydroxyphenyl) propionate] methane, 4,4,1-isopropylidene diphenol, stearyl (3,5) -Di-tert-butyl_4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3 , 5-Di-tert-butyl-1-hydroxyphenyl) propioic acid amide], 2,2'-methylenebis (4-ethyl-1-6-tert-butylphenol, 4,4,1-butylidenebis (6-tert-butyl-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3—tris (2-methyl-1) 4—Hydroxy-1-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-4-methyl-6- (2-hydroxy-1-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate 1,3,5-tris (3,5-di-tert-butyl-1-hydroxybenzyl) isocyanurate 1,3,5-tris (3,5-di-tert-butyl-1-4-hydroxybenzyl) -1,2,4,6-trimethylbenzene, 2-tert-butyl-1-4-methyl-1-5-methyl Benzyl) phenol. In addition, 2,6-diphenyl-14-octadecoxy xyphenol can be used as a phenol compound in the present invention.

By adding 0.01 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight of the phosphite compound to 100 parts by weight of the fusibinylidene-based resin, the vinylidene fluoride-based resin is Thermal stability is improved and no coloring occurs during molding. However, as shown in the comparative examples described below, when the phosphite compound is less than 0.01 parts by weight and when the phosphite compound is more than 0.5, there is no heat stabilizing effect, and coloring or foaming phenomenon occurs at the processing temperature. Happens.

Further, by using a phenol compound in addition to the phosphite compound, the thermal stability is further improved, and when the heat history is large, for example, when processing at a high temperature, it is preferable to use the phenol compound in combination.

Further, when the phosphite compound is lacking even when the phenol compound is added, the phenol compound itself is undesirably colored due to decomposition.

The amount of the phenol compound to be added is preferably not more than 10 times by weight of the phosphite compound, more preferably more than the phosphite compound and not more than 8 times by weight of the phosphite compound, more preferably 2 to 6 times by weight of the phosphite compound. is there.

When the ratio of the phenol compound to the phosphite compound is equal to or less than that of the phosphite compound, the effect of adding the phenol compound is not sufficiently exhibited. On the other hand, if the amount exceeds 10 times by weight, the phenol compound present in a large amount is decomposed, and conversely, the degree of foaming and coloring increases.

The vinylidene fluoride-based resin composition as described above can be molded into various molded products such as films, sheets, and fibers, and molded products can be obtained without fear of foaming and coloring at the processing temperature. As the molding method, compression molding, injection molding, extrusion molding, blow molding and other ordinary molding operations are performed at a molding temperature of 200 to 350 ° C. Shaped. In the molding process, the amount ratio is selected within the above composition range according to the target molded product.

In the molding process, other processing aids usually used for the molding process of the vinylidene fluoride resin, such as a lubricant and a pigment, may be added.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In the following Examples and Comparative Examples, bis- (2,6-di-tert-butyl-1.4-methylphenyl) -pentaerythritol diphosphite was used as the phosphite compound, and tetrakis-l- [methylene mono) was used as the phenol compound. 3- (3 ', 5,1-ditert-butyl-4'-hydroxyphenyl) propionate] methane was used.

Examples 1 and 2 and Comparative Examples 1 to 3

i _nh Chikaraku 1. 3 dl / g for Futsui spoon vinylidene homopolymer first and said polymer one 1 0 0 by weight parts per a composition comprising a Hosufuai bets compound addition amount shown in Table 1 2 4 0 ° C A sheet of 5 cm x 5 cm and a thickness of 1 mm was prepared under the following conditions and subjected to a thermal stability test.

In the test, the sheet was sandwiched between hot plates, and after heating at 280 ° C. or 300 ° C. for a certain period of time, the change in hue and the degree of foaming were examined. Table 1 shows the results.

Table 1 Phosphite-phenol Mixing ratio Heating Heating Sample hue

1 J \ n) j A Λ)

... BD, FiF

Time

Addition amount (.c) unin)

(Parts by weight) (parts by weight)

0 .0 5 0 2 8 0 0 No change Application 1 5 No change Example 3 0 No change

1

0 .0 5 0 3 0 0 0 No change Al 5 No change Example 30 Yellow-brown

2 Ratio 0 0 2 8 0 0 No change

1 5 4 says

Red Example 3 0 Black-brown 1 Ratio 0.0 5 0 2 8 0 0 No change

2 Ratio 1, 0 0 2 8 0 0 No change Comparison 15 Foaming Example 3 0 Foaming 3 Examples 3 and 4 and Comparative Examples 4 and 5

A composition comprising a vinylidene fluoride homopolymer having a 77, nh of 1.3 dl / g and a phosphite compound and a phenol compound in an amount shown in Table 2 with respect to 100 parts by weight of the polymer was prepared. The sheet was pressed at 0 ° C to prepare a sheet with a size of 5 cm x 5 cm and a thickness of 1 m2, and a thermal stability test was performed.

In the test, the sheet was sandwiched between hot plates and heated at 280 ° C. or 300 ° C. for a certain period of time to examine changes in hue and foaming. Table 2 shows the results.

Table 2 Phosphite-phenol Mixing ratio Heating Heating Sample hue 1 · ·

Sakusu j, rt no 1 sakusu J Λ

oJ / Dish B /

Addition amount (° C) min)

0 .5 0 .15 1: 3 2 8 0 0 No change 丽 1 5 No change Example 3 0 No change

Three

0 .5 0 .15 1: 3 3 0 0 0 No change applied 1 5 No change Example 3 0 No change 4 Ratio 0, 0 5 1.0 1: 2 0 3 0 0 0 No change

1 5 Yellowish brown Example 3 0 Reddish brown

4 Ratio 1.0 1.01: 1 3 0 0 0 No change Comparison 15 Foaming example 30 Foaming

Five Example 5

V force << 1.3 dl / g of vinylidene fluoride homopolymer 100 parts by weight, phosphite compound 0.05 parts by weight and phenol compound 0.15 parts by weight Extruded at 35 ° C from a 35mm0 extruder. This was extruded from a nozzle with a discharge diameter of 1.5 cm ø, and then cooled in water at 30 ° C to obtain a 75-monofilament. The hue of this monofilament was white and there was no change in hue due to extrusion. Comparative Example 6

7? _{I nh} Chikaraku 1. extrusion 3 dl / g of Futsui spoon vinylidene homopolymer scratch from 2 8 0 3 5mm0 press extruder. This was extruded from a nozzle having a discharge diameter of 1.5 nm0 and then cooled in water at 30 ° C. to obtain 75 / monomonofilament. The hue of this monofilament changed to reddish brown due to heating during extrusion. Industrial applicability

The vinylidene fluoride-based resin composition of the present invention is obtained by blending a specific amount of a phosphite compound with a vinylidene fluoride-based resin, and can be formed without foaming or coloring at a processing temperature. Therefore, the present invention provides a vinylidene fluoride-based resin molded product without foaming and coloring.

Claims

The scope of the claims

1. Vinylidene fluoride resin composition consisting of 100 parts by weight of vinylidene fluoride resin and 0.01 to 0.5 parts by weight of a phosphite compound and 0 to 10 parts by weight of a phenolic compound with respect to the phosphite compound object.

2. The vinylidene fluoride resin composition according to claim 1, comprising a phenol compound in an amount of 2 to 6 times by weight of the phosphite compound.

3. The vinylidene fluoride resin composition according to claim 1, wherein the phosphite compound is bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphate. .

4. The fluorinated product according to any one of claims 1 to 3, wherein the phenol compound is tetrakis [methylene-1- (3,5′-di-t-t-butyl-14′-hydroxyphenyl) propionate] methane. Vinylidene resin composition.

5. A molded article comprising the composition according to any one of claims 1 to 4.

6. A fiber comprising the composition according to any one of claims 1 to 4.

7. The molded product according to claim 5, which is molded at a molding temperature of 200 to 350 ° C.

8. The fiber according to claim 6, wherein the fiber is molded at a molding temperature of 200 to 350 ° C.