PROCESS FOR PREVENTING INJECTION MOULDED POLYOLEFIN PRODUCTS FROM FOAMING

Abstract: A polyolefin resin composition for injection molding pre­ pared by adding, to polyolefin, a condensation product be­ tween sorbitol and an aldehyde compound and a lubricant in an amount of 1/20-1/2 part by weight per part by weight of the condensation product. Polyolefin injection moldings hav­ ing excellent transparency can be obtained without foaming.

Description: Specification Polyolefin Resin Compositions for Injection Molding Field of the Invention: This invention relates to a polyolefin resin composition suitable for obtaining injection molding products with good transparency. Background of the Art: It is, hitherto, known that an improvement of a polyolefin injection molding product in transparency is attained with use of additives such as dialkyleneglycol alkyl ethers, benzenesulfonic acid esters, ammonium salt of benzenecarboxylic acid, thiodicarboxylic acids, aluminum salt of di-p-t-butylbenzoic acid, dibnzylidene- -D-sorbitol or the like. For example, condensates of sorbitol with aldehyde compounds such as dibenzylidenesorbitol or 1y3,2-4-di(methylbenzylidene)sorbitol are disclosed in Japanese Tokkyo Kdkai No. 51-22740 and No. 53-117044. These condensates are useful in improving the transparency, but there are disadvantages that foams or blisters often occur on the surface of or inside molding products so that the practical value is lost. An object of this invention is to provide polyolefin resin compositions suitable for producing injection molding products having good transparency without presenting a foaming or blistering phenomenon. Disclosure of the Invention: In accordance with this invention, there is provided a polyolefin resin composition for injection molding which comprises adding to polyolefin a condensate of sorbitol with an aldehyde compound and a lubricant of 1/20 - 1/2 parts by weight based on 1.0 part by weight of said condensate. Injection molding products of polyolefin having good transparency without bringing a foaming phenomenon are obtained by using a condensate of sorbitol with an aldehyde compound in combination with a lubricant. Best Mode for Carrying Out the Invention: The polyolefin which may be used in this invention includes propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene -butene-l random copolymer, low density ethylene polymers, ethylene-propylene random copolymer, ethylene-butene-l random copolymer, butene-l-ethylene random copolymer, butene-l-propylene random copolymer and the like. These may be used alone or in mixture of two or more. The sorbitol-aldehyde condensate which may be used in this invention is represented by the formulae, EMI3.1 wherein R1 and R2 are each a saturated or unsaturated alkyl group having 1 - 30 carbon atoms, for example, ethyl, n-hexyl, iso-hexyl, n-undecyl, 2-nonyl-2-butenyl and others; an alicyclic hydrocarbon group or its derivatives, for example, cyclohexyl, p-methyl-cyclohexyl and others; and an aromatic hydrocarbon group or its derivatives, for example, phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, p-ethylphenyl, p-hexylphenyl, l-naphthyl, l-anthryl, benzyl and so on. The following are typical examples of these condensates which may be used alone or in mixture of two or more. R1 and R2; Saturated or unsaturated alkyl groups of C1-C30: R1 and R2; 1 30 1 3-heptanylidenesorbitol, 1.3,2.4-diheptanylidenesorbitol, 1.3,2.4-di(3-nonyl-3-pentenylidene)sorbitol, Alicyclic hydrocarbon groups or derivatives thereof: 1 3-cyclohexanecarbylidenesorbitol, 1.3,2.4-dicyclohexanecarbylidenesorbitol, 1.3,2.4-di(p-methylcyclohexanecarbylidene)sorbitol, Aromatic hydrocarbon groups or derivatives thereof: 1 3-benzylidenesorbitol, 1.3,2.4-dibenzylidene-D-sorbitol, 1.3,2.4-di(m-methylbenzylidene)sorbitol, 1.3,2.4-di(p-ethylbenzylidene)sorbitol, 1.3,2.4-di(p-hexylbenzylidene)sorbitol, 1.3,2.4-di(1-naphthalenecarbylidene)sorbitol, 1.3,2.4-di(phenylacetylidene)sorbitol. A process for the synthesis of the sorbitol -aldehyde condensates is not particularly limited, though in general they are obtained by heating a mixture of sorbitol and an aldehyde compound in the presence of a dehydration catalyst such as anhydrous phosphoric acid or sulfuric acid. Such a synthesis process is disclosed in, for example, Japanese Patent Publication No. 47-7460. In the case of dibenzylidenesorbitol, 45.9 g of sorbitol, 39.8 g of benzaldehyde and 4 g of a concentrated sulfuric acid are charged to a container provided with a reflux condenser, a Liebig condenser, a liquid pouring tube (safety tube), a stirrer and a gas inlet, heated on an oil bath to 1780C and maintained at same temperature for 30 hours. Then, after cooling, the temperature is lowered to about 600C, 50 cc of methanol are added from the safety tube and the temperature is elevated to 1000C. At that time a mixture of benzaldehyde, methanol and water is effected. After completion of the effluence the reaction product mixture is cooled, poured into a large quantity of water to remove sulfuric acid and then, benzaldehyde is washed out with hot water. Thus a white solid d benzylidenesorbitol is obtained. Other condensates may be obtained in the same procedure. Also, the starting sorbitol may be the D-form, L-form or racemic-form. The sorbitol-aldehyde cdndensate may be used in the amount or preferably, 0.05 - 2.0 parts, more preferably 0.1 - 1.0 parts by weight based on 100 parts by weight of polyolefin. With an amount of less than 0.05 parts, the effect of improving transparency is hardly attained, whereas with an amount of more than 2.0 parts the effect of improving transparency is reduced on the contrary and also the product obtained becomes expensive. The lubricants which may be used are, for example, saturated or unsaturated aliphatic amides and derivatives thereof,e.g. hexic acid amide, octic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearic acid amide, lauric acid amide, behenic acid amide, methylenebisstearic acid amide, ricinoleic acid amide and so on: saturated or unsaturated aliphatic esters having 3 - 30 carbon atoms and derivatives thereof, e.g. butyl stearate, isobutyl stearate and so ont silicone compounds, e.g. a commercially available silicone mold release agent, silicone oil and so on. Mle silicone compounds are, preferably, linear organopolysiloxanes having a viscosity of 10 - 100,000 centistokes and more preferably, a straight chain dimethylpolysiloxane. these lubricants may be used alone or in mixture of two or more within the range of preferably, 1/20 to 1/2 parts and more preferably, 1/10 to 1/4 parts based on 1.0 part by weight of the sorbitol-aldehyde condensate. When the amount is less than 1/20 parts, a foam controlling effect is not attained. On the other hand, when the amount exceeds 1/2 parts, the foaming or blistering is prevented, but there are disadvantages that the effect of improvement in transparency is reduced, molds are remarkably contaminated and the cost for production of moldings becomes expensive. The composition of this invention may be used in combination with antioxidants, dyestuffs, ultraviolet absorbers and others. This invention will be illustrated by the following Examples. Example 1 and Comparative Example 1 Indicated amounts of the sorbitol-aldehyde condensate, indicated amounts of erucic acid amide and 0.1 part by weight of 2,6-di-t-butyl-4-methylphenol were mixed with 100 parts by weight of a propylene-ethylene random copolymer (ethylene content: 3.5 % by weight1 melt flow index: 15 g/10 minutes (ASTM-D-1238-62T)), which were then extruded with a 65 mm ss extruder at 250 0C to obtain pellets. The pellets obtained were formed to an injection molding sheet of 7.8 cm width x 15.7 cm length x 2 mm thickness with an injection molding machine at 250 0C and then, tested in respect of transparency and a degree of foaming. The transparency is indicated by a haze (*) (or a degree of cloudiness) measured in accordance with JIS-K 6714. The results are set forth in Table 1, which show that the process of this invention is extremely effective for the prevention of foaming. Table 1 EMI8.1 Injection <SEP> Molding <tb> Polypropylene <SEP> Composition <tb> Sheet <tb> Run <tb> No. <SEP> Sorbitol-Aldehyde <SEP> Erucic <SEP> acid <tb> PP <SEP> Condensates <SEP> amide <SEP> Haze <SEP> Degree <SEP> of <tb> wt. <SEP> part <SEP> wt. <SEP> part <SEP> wt. <SEP> part <SEP> % <SEP> Foaming <tb> Dibenzylidene-D1 <SEP> 100 <SEP> @@@bitol <SEP> 0.02 <SEP> 25.3 <SEP> No <SEP> foam <tb> 0.25 <tb> 2 <SEP> " <SEP> " <SEP> 0.05 <SEP> 26.4 <SEP> " <tb> 3 <SEP> " <SEP> " <SEP> 0.10 <SEP> 26.3 <SEP> " <tb> Ex.1 <SEP> Dibenzylidene-D4 <SEP> " <SEP> sorbitol <SEP> 0.08 <SEP> 23.0 <SEP> " <tb> 0.5 <tb> 5 <SEP> " <SEP> " <SEP> 0.20 <SEP> 23.6 <SEP> " <tb> 1.3,2.4-Di(p-ethyl6 <SEP> " <SEP> benzylidene)sorbitol <SEP> 0.02 <SEP> 18.9 <SEP> " <tb> 0.25 <tb> 7 <SEP> " <SEP> " <SEP> 0.05 <SEP> 19.2 <SEP> " <tb> 8 <SEP> " <SEP> " <SEP> 0.10 <SEP> 19.5 <SEP> " <tb> Table 1 -Continued- EMI9.1 Injection <SEP> Molding <tb> Polypropylene <SEP> Composition <tb> Sheet <tb> Run <tb> No. <SEP> PP <SEP> Sorbitol-Aldehyde <SEP> Erucic <SEP> acid <SEP> Haze <SEP> Degree <SEP> of <tb> Condensates <SEP> amide <tb> wt. <SEP> part <SEP> % <SEP> Foaming <tb> wt. <SEP> part <SEP> wt. <SEP> part <tb> 1.3,2.4-Di(p-ethyl9 <SEP> 100 <SEP> benzylidene)sorbitol <SEP> 0.08 <SEP> 17.8 <SEP> No <SEP> foam <tb> 0.5 <tb> 10 <SEP> " <SEP> " <SEP> 0.20 <SEP> 18.0 <SEP> " <tb> 1.3,2.4-Di(m-methyl Ex.1 <SEP> 11 <SEP> " <SEP> benzylidene)sorbitol <SEP> 0.02 <SEP> 23.6 <SEP> " <tb> 0.25 <tb> 12 <SEP> " <SEP> " <SEP> 0.05 <SEP> 23.9 <SEP> " <tb> 13 <SEP> " <SEP> " <SEP> 0.10 <SEP> 24.2 <SEP> " <tb> 1.3,2.4-Di(m-methyl14 <SEP> " <SEP> @@n@@@idene)sorbitol <SEP> 0.08 <SEP> 21.2 <SEP> " <tb> 0.5 <tb> 15 <SEP> " <SEP> " <SEP> 0.20 <SEP> 21.3 <SEP> " <tb> Table 1 -Continued- EMI10.1 Injection <SEP> Molding <tb> Polypropylene <SEP> Composition <tb> Sheet <tb> Run <tb> No. <SEP> PP <SEP> Sorbitol-Aldehyde <SEP> Erucic <SEP> acid <SEP> Haze <SEP> Degree <SEP> of <tb> Condensates <SEP> amide <tb> wt. <SEP> part <SEP> % <SEP> Foaming <tb> wt. <SEP> part <SEP> wt. <SEP> part <tb> 16 <SEP> 100 <SEP> - <SEP> - <SEP> 74.7 <SEP> No <SEP> foam <tb> Dibenzylidene-D- <SEP> Extremely <tb> 17 <SEP> " <SEP> sorbitol <SEP> - <SEP> 23.7 <SEP> foaming <tb> 0.5 <tb> Much <tb> 18 <SEP> " <SEP> " <SEP> 0.01 <SEP> 24.1 <tb> Comp. <SEP> foaming <tb> Ex. <SEP> 1 <tb> 1.3,2.4-Di(p-ethyl Extremely <tb> 19 <SEP> " <SEP> benzylidene)sorbitol <SEP> - <SEP> 18.2 <tb> foaming <tb> 0.5 <tb> Much <tb> 20 <SEP> " <SEP> " <SEP> 0.01 <SEP> 18.0 <tb> foaming <tb> 1.3,2.4-Di(m-methyl Extremely <tb> 21 <SEP> " <SEP> benxylidene)@orbitol <SEP> - <SEP> 21.1 <tb> foaming <tb> 0.5 <tb> Much <tb> 22 <SEP> " <SEP> " <SEP> 0.01 <SEP> 21.3 <tb> foaming <tb> Example 2 Injection molding sheets were obtained in the same procedure as in Example 1 except using a libricant set forth in Table 2 instead of erucic acid amide. The test results are given in Table 2. It is clear therefrom that the process of this invention is remarkably effective for the prevention of foaming. Table 2 EMI12.1 Injection <SEP> Molding <tb> Polypropylene <SEP> Composition <tb> Sheet <tb> Run <tb> PP <SEP> Sorbitol-Aldehyde <SEP> Lubricants <SEP> Haze <SEP> Degree <SEP> of <tb> No. <tb> Condensates <tb> wt. <SEP> part <SEP> wt. <SEP> part <SEP> % <SEP> Foaming <tb> wt. <SEP> part <tb> Dibenzylidene-D Oleic <SEP> acid <SEP> amide <tb> 1 <SEP> 100 <SEP> sorbitol <SEP> 23.6 <SEP> No <SEP> foam <tb> 0.08 <tb> 0.5 <tb> Stearic <SEP> acid <SEP> amide <tb> 2 <SEP> " <SEP> " <SEP> 24.1 <SEP> " <tb> 0.08 <tb> Erucic <SEP> acid <SEP> amide: <tb> Oleic <SEP> acid <SEP> amide: <tb> Ex. <SEP> 2 <SEP> 3 <SEP> " <SEP> " <SEP> Stearic <SEP> acid <SEP> amide <SEP> 23.0 <SEP> " <tb> =90:5:5 <SEP> (wt.ratio) <tb> 0.08 <tb> Butyl <SEP> stearate <tb> 4 <SEP> " <SEP> " <SEP> 23.8 <SEP> " <tb> 0.08 <tb> Silicone <SEP> oil <SEP> * <tb> 5 <SEP> " <SEP> " <SEP> 24.5 <SEP> " <tb> 0.08 <tb> 1.3,2.4-Di(p-ethyl Oleic <SEP> acid <SEP> amide <tb> 6 <SEP> " <SEP> benzylidene)sorbitol <SEP> 18.0 <SEP> " <tb> 0.08 <tb> 0.5 <tb> Table 2 -Continued- EMI13.1 Injection <SEP> Moding <tb> Polypropylene <SEP> Composition <tb> Sheet <tb> Run <tb> PP <SEP> Sorbitol-Aldehyde <SEP> Lubricants <SEP> Haze <SEP> Degree <SEP> of <tb> No. <tb> Condensates <tb> wt. <SEP> part <SEP> wt. <SEP> part <SEP> % <SEP> Foaming <tb> wt. <SEP> part <tb> 1.@,2.4-Di(p-ethyl Stearic <SEP> acid <SEP> amide <tb> 7 <SEP> 100 <SEP> benzylidene)sorbitol <SEP> 18.2 <SEP> No <SEP> foam <tb> 0.08 <tb> 0.5 <tb> Erucic <SEP> acid <SEP> amide: <tb> Oleic <SEP> acid <SEP> amide: <tb> 8 <SEP> " <SEP> " <SEP> Stearic <SEP> acid <SEP> amide <SEP> 18.0 <SEP> " <tb> =90:5: :5 <SEP> (wt.ratio) <tb> Ex.2 <SEP> 0.08 <tb> Butyl <SEP> stearate <tb> 9 <SEP> " <SEP> " <SEP> 18.5 <SEP> " <tb> 0.08 <tb> Silicone <SEP> oil <SEP> * <tb> 10 <SEP> " <SEP> " <SEP> 18.8 <SEP> " <tb> 0.08 <tb> 1.3,2.4-Di(m-methyl Oleic <SEP> acid <SEP> amide <tb> 11 <SEP> " <SEP> benzylidene)sorbitol <SEP> 21.5 <SEP> " <tb> 0.08 <tb> 0.5 <tb> Butyl <SEP> stearate <tb> 12 <SEP> " <SEP> " <SEP> 21.2 <SEP> " <tb> 0.08 <tb> * TSM 451-200, the tradename by Toshiba Silicone Ltd., Japan Industrial Applicability: As described above, when the compositions of this invention are subject to injection molding, the transparency of the moldings is remarkably improved without presenting a foaming phenomenon and thus, transparent moldings having a good appearance are obtained.

Claims: Scope of Claims: 1. A polyolefin resin composition for injection molding which comprises adding to polyolefin a condensate of sorbitol with an aldehyde compound and a lubricant of 1/20 to 1/2 parts by weight based on 1.0 part by weight of said condensate. 2. The resin composition of claim 1 wherein the condensate content is comprised between 0.05 and 2 parts by weight based on 100 parts by weight of the polyolefin. 3. The resin composition of claim 1 wherein said condensate is at least one of members represented by the formulae, EMI15.1 and EMI16.1 wherein R1 and R2 each is a saturated or unsaturated alkyl group of 1 to 30 carbon atoms, an alicyclic hydrocarbon group or its derivatives, or an aromatic hydrocarbon group or its derivatives. 4. The resin composition of claim 1 wherein said lubricant is at least one of members selected from the group consisting of a saturated or unsaturated aliphatic amide having 3 - 30 carbon atoms and its derivatives, a saturated or unsaturated aliphatic ester having 3 - 30 carbon atoms and its derivatives and a silicone compound.

Inventors: DOI, HIROYUKI, INOUE, TAKEO, OTSU, JUN, SASAKI, TATEYO, SUEHIRO, KEIGO
Applicants: MITSUI TOATSU CHEMICALS, INCORPORATED
Application year: 1979
Main classification: C08L23
IPC codes: C08L101, C08K5, C08L21, C08L83, C08L51, C08L87, C08L77, B29C45, C08L23, C08L7