JPH08134293A - Polypropylene resin composition - Google Patents

Abstract

PURPOSE: To prepare a polypropylene resin compsn. which has excellent transparency and bleedout property by incorporating a particular sorbitol compd., a particular polyhydric alcohol monoester, and a particular N-contg. compd. in a predetermined crystalline propylene polymer. CONSTITUTION: 0.01 to 1 pt.wt. sorbitol compd. represented by the formula I (wherein R is a 1-8 C alkyl, an alkoxy, a halogen, or OH; m and n are 0 to 3), 0.01 to 1 pt.wt. 11-18 C polyhydric alcohol mono ester (A), and an N-contg. compd. represented by the formula II [wherein R<1> is a 6-22 C alkyl or an alkenyl; X is a group selected from groups represented by the formulae III to IV; Y and Z are -CH2 CH2 O-, -CH2 -CH(CH3 )-O-, or -CH2 -CH(CH2 OH)-O-; and m+n is 2 to 5] in an amt. of 0.05 to 0.9 in terms of the wt. ratio thereof to the component (A) are incorporated into 100 pts.wt. crystalline propylene polymer having a melt flow rate of 0.5 to 100g/10min and an ethylene content of 0 to 6wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition suitable for producing an injection molded product or an extrusion molded product having excellent transparency.

[0002]

2. Description of the Related Art Among various thermoplastic general-purpose resins, crystalline propylene polymers are widely used as one of the most versatile plastic materials in terms of physical properties, molding processability, price and the like.

As a method for improving the transparency of polypropylene, a method of random copolymerization with ethylene or a method of blending a nucleating agent (crystallization accelerator) is known, but the transparency is improved only by random copolymerization. The effect is not sufficient, and there is a drawback that the rigidity and heat resistance are significantly reduced. On the other hand, the compounding of a nucleating agent is effective in improving transparency, rigidity and heat resistance, and is an effective method.

The crystalline propylene polymer is prepared by adding a transparent nucleating agent typified by a sorbitol compound,
Although it exhibits excellent transparency, its transparency is not stable because it changes depending on the polymerization method of the polymer and the catalyst.

It is considered that the cause is that the action of the transparent nucleating agent is inhibited by the catalyst residue. As a means for improving this, there are methods such as increasing the amount of the transparent nucleating agent and increasing the ethylene content, but there are problems in terms of cost increase, mold contamination, odor deterioration, safety and hygiene, etc. In addition, when the ethylene content is increased, there is a problem that the flexural modulus is extremely deteriorated.

[0006]

SUMMARY OF THE INVENTION The present invention solves such problems and has excellent transparency and bleed-out property without changing the amount of the transparent nucleating agent and without impairing rigidity and heat resistance. It aims at providing the propylene resin composition which improved.

[0007]

Means for Solving the Problems As a result of studying various additive formulations in order to solve the above-mentioned problems,
The present invention has been accomplished by finding that the above problems can be solved by blending a crystalline propylene polymer with a specific additive.

That is, the present invention has a melt flow rate of 0.5 to 100 g / 10 minutes and an ethylene content of 0 to 6
A sorbitol-based compound represented by the following general formula (I) 0.0
1 to 1 part by weight, 0.01 to 1 part by weight of a polyhydric alcohol monoester having 11 to 28 carbon atoms, and a weight ratio of 0.05 to 0.9 with respect to the polyhydric alcohol monoester, A polypropylene resin composition comprising a nitrogen-containing compound represented by the general formula (II).

[0009]

Embedded image (In the formula, R is an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom or a hydroxyl group, and may be different in the same compound. M and n are independently 0 to 3 It is an integer.)

[Chemical 4] In the present invention, the crystalline propylene polymer serving as a base is a melt flow rate (MFR; JIS K
7210; load 2.16 kg, measured at 230 ° C.) is 0.
Range of 5 to 100 g / 10 minutes, preferably 10 to 80 g
A propylene homopolymer in the range of / 10 minutes or a propylene-ethylene random copolymer having an ethylene content of 6 parts by weight or less (hereinafter sometimes referred to as polypropylene resin) is used.

When the melt flow rate is out of the above range, the moldability is deteriorated, which is not preferable.

The method for producing the polypropylene resin is not particularly limited, but generally, a catalyst component containing titanium trichloride as a main component or a transition metal compound catalyst component such as titanium trichloride or titanium tetrachloride is used. It is produced using a highly active catalyst prepared by combining a catalyst component supported on a carrier containing magnesium halide as a main component such as magnesium chloride and an organoaluminum compound such as triethylaluminum and diethylaluminum chloride.
In particular, the catalyst using the catalyst component supported on the above carrier has a high catalytic activity, and the prepared polypropylene resin is not substantially decatalyzed.

The sorbitol compound used in the present invention has the general formula (I):

Embedded image (In the formula, R is an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom or a hydroxyl group, and may be different in the same compound. M and n are independently 0 to 3 It is a compound represented by an integer.

Specific examples of R in the above general formula include:
As an alkyl group, methyl, ethyl, n-propyl, i
-Propyl, n-butyl, t-butyl and the like, alkoxy groups such as methoxy, ethoxy and i-propoxy,
Examples of the halogen atom include chlorine and bromine.

Examples of the sorbitol compounds include dibenzylidene sorbitol, (1,3) 2,4-
Di (p-methylbenzylidene) sorbitol, (1,
3) 2,4-di (p-chlorobenzylidene) sorbitol, (1,3) 2,4-di (p-methoxybenzylidene) sorbitol, (1,3) 2,4-di (p-ethylbenzylidene) sorbitol , (1,3) 2,4-di (pn-propylbenzylidene) sorbitol,
(1,3) 2,4-di (pt-butylbenzylidene)
Sorbitol, (1,3) 2,4-di (p-ethoxybenzylidene) sorbitol, (1,3) 2,4-di (p
-I-propoxybenzylidene) sorbitol, (1,
3) 2,4-di (m-methylcybenzylidene) sorbitol and the like.

Particularly, (1,3) 2,4-di (p-methylbenzylidene) sorbitol is preferable.

The amount of the sorbitol-based compound added is 0.01 to 1 with respect to 100 parts by weight of the polypropylene-based resin.
Parts by weight, preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.25 parts by weight. If it exceeds 1 part by weight, not only is it economical, but problems such as bleed out occur.

Examples of the polyhydric alcohol monoester used in the present invention include glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monooleate and diglycerin monolaurate. Rate, diglycerin monomyristate, diglycerin monopalmitate, diglycerin monostearate,
Examples thereof include diglycerin monobehenate, diglycerin monooleate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate and sorbitan monobehenate.

Of these, glycerin monostearate, glycerin monopalmitate or sorbitan monostearate are preferable, and glycerin monostearate is particularly preferable.

The amount of polyhydric alcohol monoester added is
0.01 to 100 parts by weight of polypropylene resin
It is 1 part by weight, preferably 0.05 to 0.5 part by weight, particularly preferably 0.05 to 0.25 part by weight.

If the amount added is less than 0.01 parts by weight, the transparency and bleed out are not improved. Further, if it exceeds 1 part by weight, a whitening phenomenon occurs, which is not preferable.

The nitrogen-containing compound used in the present invention is a compound represented by the following general formula (II).

[0022]

[Chemical 6] Examples of the nitrogen-containing compound include lauryldiethanolamine, myristyldiethanolamine, palmityldiethanolamine, stearyldiethanolamine, oleyldiethanolamine, lauryldiisopropanolamine, myristyldiisopropanolamine, palmityldiisopropanolamine, stearyldiisopropanolamine, oleyldiisopropanolamine. Or lauryldiethanolamide, myristyldiethanolamide, palmityldiethanolamide, stearyldiethanolamide, behenyldiethanolamide, oleyldiethanolamide, lauryldiisopropanolamide, myristyldiisopropanolamide, palmityldiisopropanolamide,
Examples thereof include amides such as stearyldiisopropanolamide and oleyldiisopropanolamide.

Of these, stearyldiethanolamine, lauryldiethanolamine or stearyldiethanolamide are preferable, and stearyldiethanolamine is particularly preferable.

The amount of the nitrogen-containing compound added is 0.05 to 0.
9, preferably 0.05 to 0.7, particularly preferably 0.
It is a ratio of 1 to 0.5.

If the amount added is less than 0.05 by weight relative to the polyhydric alcohol monoester, the transparency and bleed-out cannot be improved. Further, if it exceeds 0.9, a whitening phenomenon occurs, which is not preferable.

The polypropylene resin composition of the present invention contains, in addition to the above-mentioned components, phenol-based, sulfur-based and phosphorus-based antioxidants, inorganic fillers, and ultraviolet rays within the range not impairing the object of the present invention. Other additives such as an absorber, a light stabilizer, an antifogging agent, an antiblocking agent, a lubricant, a pigment and a dye can be added.

The phenolic antioxidant is a hindered phenolic compound in which the ortho position to the OH group is a t-butyl group or a methyl group, both of which are the same or significantly different, or only one of the ortho positions is present. The thing which is a hydrogen atom is mentioned. As an example, 2,6-di-t
-Butyl-P-cresol, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,3. 5-tris (4-t-butyl-3
-Hydroxy-2,6-dimethylbenzyl), 1,3
5-triazine-2,4,6- (1H-3H-5H)-
Trione, pentaerythritol tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-
2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl-2,4
8,10-Etraoxaspiro [5,5] undecane and the like can be mentioned.

As the sulfur-based antioxidant, a dialkylthiopropionic acid ester having an alkyl group of 1 carbon atom is used.
2 to 18 and polyhydric alcohol esters of alkylthiopropionic acid having an alkyl group of 4 to 18 carbon atoms. Preferred examples include pentaerythritol tetrakis (β-lauryl-thiodipropionate), distearyl-3,3′-thiodipropionate, dilauryldithiodipropionate, dimyristylthiodipropionate, distearyldithiodipropionate. Examples thereof include pionate and lauryl stearyl thiodipropionate.

Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite and bis (2,4,4)
6-tri-t-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'- Biphenylene phosphite, cyclic neopentane tetrayl bis (2,4
-Di-t-butylphenylphosphite), bis (2,2
6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphite, trisnonylphosphite, trisphenylphosphite , Tris tridecyl phosphite, tris (monononylphenyl) phosphite, tris (mono,
Dinonylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2,4-di-t)
-Butyl-5-methylphenyl) phosphite, tris (2,5-di-t-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) ) Phenyl] phosphite, tris [2,4-di- (1,1-dimethylpropyl) phenyl] phosphite, tris (2-cyclohexylphenyl) phosphite, trisphenylphosphite, tris (octylthioethyl) phosphite ,
Tris (octylthiopropyl) phosphite, Tris (cresylthiopropyl) phosphite, Tris (3-
5-di-t-butyl-4-hydroxyphenyl) phosphite, 4,4'-butylidene-bis (3-methyl-)
4,6-di-t-butylphenyl-di-tridecyl) phosphite, 4,4'-butylidene-bis (3-methyl-4,6-di-t-butylphenyl-di-octyl) phosphite, 1 , 1,3-Tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, bis (2,4-di-t-butylphenyl) spiropentaerythritol diphosphite, bis (2 , 6-
Di-t-butyl-4-methylphenyl) spiropentaerythritol di-phosphite, bis (2,6-di-t
-Butyl-4-ethylphenyl) spiropentaerythritol-diphosphite, bis (2,4,6-tri-t
-Butylphenyl) spiropentaerythritol-diphosphite and other phosphite compounds, tetrakis (2,4-di-t-butylphenyl) -4,4 'biphenylene-diphosphonite, tetrakis (2,4-di-t)
Examples include phosphonite compounds such as -butyl-5-methylphenyl) -4,4'-biphenylenephosphonite.

The amount of the above-mentioned phenol-based, phosphorus-based, and sulfur-based antioxidants used is generally polypropylene resin 1
0.001 to 2 parts by weight, preferably 0.00
It is from 01 to 1 part by weight.

The polypropylene resin composition of the present invention contains
It is also possible to use neutralizing agents.

As the neutralizing agent, metal soaps, hydrotalcites, calcium aluminum silicate, metals of Group II of the periodic table and oxides of metals such as zinc, aluminum, tin and lead, and water can be used. Mention may be made of oxides. As the neutralizing agent (which also serves as a dispersant), it is particularly preferable to use metal soap or hydrotalcite. Examples of the metal soap include metal salts of higher fatty acids or fatty acid oxyacids with metals such as magnesium, calcium, barium, zinc, aluminum, tin and lead. Examples of higher fatty acids include chain monocarboxylic acids having 10 to 22 carbon atoms, and stearic acid, lauric acid and the like are preferable. Examples of the fatty acid oxyacid include those having an alcoholic hydroxyl group in the side chain of an aliphatic carboxylic acid, and lactic acid, citric acid, hydroxystearic acid and the like are preferable. Preferred examples of the metal soap include magnesium stearate, calcium stearate, barium stearate, zinc stearate, aluminum stearate, calcium citrate, calcium lactate, calcium 12-hydroxystearate, calcium stearyl lactate, calcium lauryl lactate and the like. To be Hydrotalcites do not contain water-containing basic carbonates such as magnesium, calcium, zinc, aluminum, bismuth, or water of crystallization, and include natural products and synthetic products. As a natural product, Mg ₆ Al ₂ (OH) ₁₆ CO
_{One having} a structure of 3.4H ₂ O can be mentioned. Further, as a synthetic product, Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15
・ 0.54H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃・
3.5H ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ , Z
_{n 6 Al 2 (OH) 16} CO 3 · 4H 2 O, Ca 6 Al 2
_{(OH) 16 CO 3 · 4H} 2 O, Mg 14 Bi 2 (OH)
_29.6 (CO ₃ ) _2.2 · 4.2H ₂ O and the like. As oxides and hydroxides of metals of Group II of the periodic table, magnesium oxide, calcium oxide, zinc oxide, calcium hydroxide, aluminum hydroxide, magnesium hydroxide and the like are particularly preferable.

The amount of the neutralizing agent used is usually 0.01 to 1 part by weight based on 100 parts by weight of the polypropylene resin.

[0034]

EXAMPLES The present invention will now be described in more detail with reference to examples. The percentages (%) in the examples are by weight unless otherwise specified.

Example 1 A propylene-ethylene random copolymer obtained by using a Mg-supported catalyst (manufactured by Tonen Kagaku Co., ethylene content 2.8%, MFR 20 g / 10).
Min,) 100 parts by weight, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba-Geigy, trade name Irganox1010) (Ir1010) 0.05 parts by weight Part, tris (2,4-di-t-butylphenyl) phosphite (Asahi Denka Kogyo KK, trade name Mark 2112).
05 parts by weight, calcium stearate (Ca-St)
0.05 parts by weight, (1,3) 2,4-di (paramethylbenzylidene) sorbitol (Shin Nippon Rika Co., Ltd., trade name Gelol MD) 0.20 parts by weight, glycerin monostearate (GMS) 0.14 Parts by weight and 0.06 parts by weight of stearyldiethanolamine (STDEA) were dry blended with a supermixer, and then pelletized using a 50 mmφ extruder (L / D = 28). A test piece according to the following test method was molded from the pellet by an injection molding machine. The physical properties of this test piece were measured according to the following test methods, and the results are shown in Table 1.

(1) Haze: ASTM D-1003,
Thickness 2 mm (2) Bleed-out property evaluation: test piece (80 mm x 80
(mm × 2 mm) is kept in an air oven at 80 ° C. for 2 hours, and then the deterioration of transparency and the stickiness of the surface are visually determined (a part of the test piece is wiped off, and the other parts are compared). ... Stickiness or whitening of surface
Δ: Stickiness or slight whitening of the surface (Example 2, Comparative Examples 1 to 4) Except that STDEA or GMS was not used, or both were not used, or both were used by changing the use ratio of both. Dry blending was carried out in the same manner as in Example 1 to obtain pellets. Physical properties of the test pieces obtained from these pellets were measured in the same manner as in Example 1, and the results are shown in Table 1.

[0037]

[Table 1] Example 3 A propylene-ethylene random copolymer obtained by using a catalyst component containing titanium trichloride as a main component (manufactured by Tonen Kagaku Co., Ltd., ethylene content 3.2%, MFR15).
g / 10 min) was used as the polypropylene resin, and dry blending was performed in the same manner as in Example 1 to obtain pellets. The physical properties of the test pieces obtained from the pellets were measured in the same manner as in Example 1, and the results are shown in Table 2.

(Example 4, Comparative Examples 5 to 8) Dry blending was performed in the same manner as in Example 2 and Comparative Examples 1 to 4 except that the polypropylene resin used in Example 3 was used and pelletized. Got Physical properties of the test pieces obtained from these pellets were measured in the same manner as in Example 1,
The results are shown in Table 2.

[0039]

[Table 2] (Examples 5 and 6) GMS and S used in Example 1
Table 3 shows glycerin monopalmitate (GMP) or sorbitan monostearate (SMS) as the polyhydric alcohol monoester instead of TDEA, and lauryl diethanolamine (LADEA) or stearyl diethanolamide (STDAD) as the nitrogen-containing compound. Pellets were obtained by dry blending in the same manner as in Example 1 except that the pellets were used. Physical properties of test pieces obtained from these pellets were measured in the same manner as in Example 1, and the results are shown in Table 3.

(Examples 7 and 8) Example 5 was repeated except that the polypropylene resin used in Example 3 was used.
Dry blending was performed in the same manner as in Nos. 6 and 6 to obtain pellets. Physical properties of test pieces obtained from these pellets were measured in the same manner as in Example 1, and the results are shown in Table 3.

[0041]

[Table 3]

[0042]

Industrial Applicability According to the present invention, it is possible to provide a polypropylene resin composition having excellent transparency and less bleed out. This polypropylene resin composition, in the field of molded products produced by injection molding or extrusion molding,
Particularly useful.

Claims (6)

[Claims] 1. A melt flow rate of 0.5 to 100 g.
/ 10 minutes, 0.01 to 1 part by weight of a sorbitol-based compound represented by the following general formula (I), and 100 to 11 parts by weight of a crystalline propylene polymer having an ethylene content of 0 to 6% by weight and 11 to 11 carbon atoms. 18 polyhydric alcohol monoesters 0.01-
1 part by weight and a weight ratio of 0.05 to 0.9 with respect to the polyhydric alcohol monoester, the following general formula (II)
A polypropylene resin composition containing a nitrogen-containing compound represented by. Embedded image (In the formula, R is an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom or a hydroxyl group, and may be different in the same compound. M and n are independently 0 to 3 It is an integer.) 2. The polypropylene resin composition according to claim 1, wherein the polyhydric alcohol monoester is glycerin monostearate, glycerin monopalmitate or sorbitan monostearate. 3. The polypropylene resin composition according to claim 1, wherein the nitrogen-containing compound is stearyldiethanolamine, lauryldiethanolamine or stearyldiethanolamide. 4. The polypropylene resin composition according to claim 1, wherein the polyhydric alcohol monoester is glycerin monostearate, and the nitrogen-containing compound is stearyl diethanolamine. 5. The blending amount of the sorbitol-based compound is 0.
0.05 to 0.5 parts by weight, the amount of the polyhydric alcohol monoester compounded is 0.05 to 0.5% by weight, and the ratio of the compounding weight ratio of the nitrogen-containing compound to the polyhydric alcohol monoester is 0. The polypropylene resin composition according to any one of claims 1 to 4, wherein the polypropylene resin composition is 0.05 to 0.7. 6. The blending amount of the sorbitol compound is 0.
1 to 0.25 part by weight, the amount of the polyhydric alcohol monoester blended is 0.05 to 0.25 part by weight, and the blending weight ratio ratio of the nitrogen-containing compound to the polyhydric alcohol monoester is 0. It is 0.1-0.5, The polypropylene resin composition in any one of Claims 1-4.