JP2766330B2 - Crystalline polymer material composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a crystalline polymer material composition,
The present invention relates to a crystalline polymer material composition having improved processability, strength, transparency and the like by adding a bisphenol cyclic acidic phosphate and an alkali metal salt of a higher fatty acid.

[Problems to be solved by conventional technology and invention]

Since crystalline polymer materials such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, and polyamide have a low crystallization rate after heat molding, molding cycleability is low and the mold temperature must be lowered. In addition, there is a disadvantage that the film shrinks due to crystallization after heat molding. In addition, these crystalline polymer materials have disadvantages of insufficient strength and poor transparency because large crystals are generated.

All of these drawbacks are derived from the crystallinity of the polymer material, and are known to be eliminated if the crystallization temperature of the polymer material can be increased and fine crystals can be rapidly generated. .

For this purpose, it is known to add a nucleating agent or a crystallization accelerator. Conventionally, metal salts of carboxylic acids such as aluminum p-tert-butylbenzoate, sodium adipate, sodium bis ( Acid phosphate metal salts such as 4-tert-butylphenyl) phosphate and sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate; dibenzylidene sorbitol; bis (methylbenzylidene) sorbitol; Polyhydric alcohol derivatives and the like have been used.

Among these compounds, metal salts of cyclic phosphate esters of alkylidene bisphenols described in JP-A-58-1736 and JP-A-59-184252 have relatively large effects and are widely used. ing.

However, the effect of the compound may still be insufficient, and a method using a combination of an aluminum salt of p-tert-butylbenzoic acid and an alkali metal salt or zinc salt of a higher aliphatic carboxylic acid (JP-A-62-263244) Gazette, JP-A-63-12
No. 5551) has been proposed, but it has not been sufficient yet, and practical improvement has been demanded.

[Means for solving the problem]

The present invention and the like have conducted intensive studies to eliminate the inadequate effect of the metal salt of a cyclic phosphate of alkylidene bisphenols. As a result, the cyclic acidic phosphate of alkylidene bisphenols and the alkali metal of higher fatty acids The present inventors have found that an effect which has not been seen so far appears by adding a salt, and completed the present invention.

That is, the present invention relates to the present invention provides 0.005 to 5 parts by weight of a cyclic acidic phosphate represented by the following general formula (I) and an alkali metal salt of a higher fatty acid with respect to 100 parts by weight of a crystalline polymer material excluding a polypropylene resin. It is intended to provide a crystalline polymer material composition to which 0.005 to 5 parts by weight is added.

(In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an alkyl group having 1 to 9 carbon atoms.) In the general formula (I), R ₁ represents Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Isobutyl and the like, having 1 carbon atom represented by R ₂
Examples of the alkyl group of ~ 9 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl and the like.

Among these compounds, compounds in which R ₁ is a hydrogen atom or a methyl group and R ₂ is an alkyl group having 1 to 4 carbon atoms are particularly preferred.

Accordingly, the following compounds are particularly preferable as the compound represented by the above general formula (I) used in the present invention.

The cyclic acid phosphate compound represented by the above general formula (I) used in the present invention is produced, for example, by reacting phosphorus oxychloride with 2,2'-alkylidenebisphenol and then hydrolyzing the same, followed by filtration, It is dried to obtain the desired product, and if necessary, it is pulverized and used as a crystal nucleating agent.

The alkali metal salt of a higher fatty acid used in combination with the above-mentioned cyclic acidic phosphoric acid ester compound includes carbon atoms.
Lithium, sodium, and potassium salts of 12 to 30 higher fatty acids are preferable, and alkali metal salts of saturated higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and montanic acid are particularly preferable.

Examples of the crystalline polymer material that is the object of the present invention include, for example, thermoplastic polymers such as polyethylene, polybutene-1, α-olefin polymers such as poly-3-methylbutene, polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate. Examples include straight-chain polyamides such as straight-chain polyesters, polycaprolactam, and polyhexamethylene adipamide.

In the present invention, the method of adding the compound represented by the general formula (I) to the crystalline polymer material is not particularly limited, and a generally used method can be applied as it is. For example, a method of dry blending a crystalline polymer material powder or a pellet with an additive powder can be used.

Further, the crystalline polymer material composition of the present invention can be used for various molded articles, fibers, biaxially stretched films, sheets and the like.

The composition of the present invention may contain, if necessary, a phenolic antioxidant, a thioether-based antioxidant, a phosphite-based antioxidant, an ultraviolet absorber, a light stabilizer, a heavy metal deactivator, a metal soap, a pigment. , A filler, an organotin compound, a plasticizer, an epoxy compound, a foaming agent, an antistatic agent, a flame retardant, a lubricant, a processing aid, and the like.

〔Example〕

Next, the present invention will be specifically described with reference to examples. However, the invention is not limited by these examples.

Example 1 After kneading rolls at 160 ° C. for 5 minutes,
Compression molding at 200 ℃ / cm ² for 5 minutes, then 60 ℃
It was quenched to prepare a test piece having a thickness of 1 mm.

Using this test piece, the haze value was measured based on ASTM D-1033-61.

 Table 1 shows the results.

<Blending> Polyethylene (Mirason Neo23H) 100 parts by weight 4,4-thiobis (3-methyl-6-tert-butylphenol) 0.1 Cyclic acid phosphate (No. 4) 0.2 Higher fatty acid alkali metal salt 0.1 (Table 1) Example 2 To 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.66, 0.1 part by weight of sodium stearate and 0.5 part by weight of a sample (cyclic acid phosphate or a comparative sample) shown in Table 2 were mixed, and then a twin-screw extruder was used. Was used to make a pellet. Put the pellet in a differential calorimeter
/ Min, and the crystallization temperature during the heating was measured.

After melting at 300 ° C. for 5 minutes, the crystallization temperature when the temperature was lowered at 16 ° C./minute was measured, and the ratio H between the height H of the endothermic peak at the time of temperature decrease and the width W at H / 2 was measured. / W was determined.

The lower the crystallization temperature at the time of heating, the higher the degree of crystallization when a low-temperature mold is used.The higher the crystallization temperature at the time of cooling, and the higher the H / W, the higher the crystallization speed. Indicates that it is big.

 The results are shown in Table 2 below.

Example 3 Potassium stearate was added to 100 parts by weight of nylon-6 resin.
Dry blending 0.1 part by weight and 0.1 part by weight of the sample shown in Table 3 (cyclic acid phosphate or comparative sample)
Injection molding using a 3.5 oz. In-line screw injection molding machine (cylinder temperature: 220, 240, 240, 235 ° C.) using a mold for a disc-shaped molded product having a thickness of 10 mm and a diameter of 100 mm at a mold temperature of 80 ° C. did.

Injection time is 14 seconds, intermediate time is 4 seconds, cooling time is shortened sequentially from 50 seconds, and 30 shots are molded. Cooling time when it is difficult to release from the mold or when warping or sink occurs in the molded product Was measured.

The shorter the cooling time is, the shorter the molding cycle can be, which is preferable in the working operation.

 Table 3 shows the results.

[Effects of the Invention] As is clear from the above Examples, the transparency and mechanical properties of the crystalline polymer material are improved by using a specific cyclic acidic phosphate ester of the present invention and an alkali metal salt of a higher fatty acid in combination. Not only can the improvement be significant, but also the molding cycle can be improved.

Continuation of the front page (56) References JP-A-3-79649 (JP, A) JP-A-59-113046 (JP, A) JP-A-61-210090 (JP, A) (58) Fields studied (Int .Cl. ⁶ , DB name) C08L 101/00-101/14 C08K 5/09-5/098 C08L 23/00-23/36 C08L 67/00-67/08 C08L 77/00-77/12 C08K 5 / 51-5/527 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A cyclic acid phosphate represented by the following general formula (I): 0.005 to 5 parts by weight and an alkali metal salt of a higher fatty acid: 0.005 to 100 parts by weight of a crystalline polymer material excluding a polypropylene resin. ~ 5 parts by weight,
A crystalline polymer material composition. (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an alkyl group having 1 to 9 carbon atoms.)