JPS5839847B2 - tenkazaigan - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thermoplastic resin molded article containing additives.

Currently, there are a large number of types of thermoplastic resins that are industrially produced, and each resin is widely used depending on its characteristics.

However, as the use of thermoplastic resins becomes broader, it is gradually becoming necessary to change or improve their properties in various ways, and one way to do this is to add additives (e.g. pigments, flame retardants, modifiers, etc.) to thermoplastic resins. It has been carried out to produce molded products with improved properties by blending them.

In order to blend additives into a thermoplastic resin, it is necessary to uniformly disperse the additives at a predetermined concentration.

Conventionally, as a method for blending additives into thermoplastic resins, a method of adding additives during the synthesis reaction of the thermoplastic resin or to reaction raw materials has been widely adopted.

However, this method has the disadvantage that the additives cause various troubles during the reaction, and furthermore, the additives contaminate the entire reaction apparatus, making it difficult to change the type of additives, and making it difficult to produce a wide variety of products in small quantities. In this case, the cost will be high.

Also known is a method in which additives are added to a thermoplastic resin after the synthesis reaction is completed and the resin is then molded.

Compared to the above-mentioned method, this method allows the type of additive to be easily changed and is advantageous in terms of cost.

However, this method also has significant drawbacks.

That is, in the method of kneading additives into a thermoplastic resin using a roll mill, Banbury mixer, etc., before molding the thermoplastic resin, it takes a long time to uniformly knead the additives into the thermoplastic resin. This often significantly impairs the quality of thermoplastic resin molded products.

In addition, the so-called dry blending method, in which thermoplastic resin is mixed with additives and then molded, is more advantageous than the melt-kneading method because there is less risk of quality deterioration due to heat, but in general, additives are mixed into the thermoplastic resin at a high level. cannot be dispersed into

This method can only be applied when the additives used are highly compatible with the thermoplastic resin, so its scope of application is very limited.

Moreover, in such a dry blending method, if a large enough industrial mixing device is used to perform the mixing, uneven mixing occurs, and the quality of the melt-molded product varies greatly, significantly reducing its value as a product. descend.

In order to compensate for these drawbacks, it may be possible to use an adhesive when mixing the additive and thermoplastic resin, but if you mix the additive, thermoplastic resin, and adhesive at the same time, the additives will adhere to each other. It cannot be expected that the additive will create agglomerates and improve the dispersibility of the additive.

The present inventor has arrived at the present invention as a result of intensive research on a method for producing thermoplastic resin molded products containing additives in a highly and uniformly dispersed state without such drawbacks, regardless of the properties of the additives. It is something.

That is, the present invention is a thermoplastic resin in which additives are blended after a thermoplastic phase JIIB having a lower melting point than the thermoplastic phase 'A'RA is melted and adhered to the surface of a granular thermoplastic resin N at a temperature below the melting point of the thermoplastic resin N. This is a method for producing an additive-containing thermoplastic resin molded product, which is characterized by mixing powders of resin (C) and then molding.

The thermoplastic resin M referred to in the present invention includes polyester, polyamide, polycarbonate, polyethylene, polypropylene, polyvinyl chloride, acrylic resin, methacrylic resin, ABS resin, AS resin, polystyrene, polybutadiene, acetate resin, etc., and a mixture thereof. There may be.

The particle size of such thermoplastic resin is such that the average diameter of the interpolated spheres is 1 to 5.
The shape may be arbitrary, such as a dice shape, a cylinder shape, or a spherical shape.

The diameter of an interpolated sphere in the present invention is expressed by converting an arbitrary shape into a sphere of the same volume and using the diameter of the sphere at that time.

The thermoplastic phase Me used in the present invention is a thermoplastic phase JII
A) is a thermoplastic resin having a melting point at least 20°C or more, preferably 30°C or more lower than the melting point of A), and the thermoplastic phase J
It does not substantially decompose at a molding temperature of 1 mA).

In addition, it is preferable to use one selected from those that are compatible with the thermoplastic phase (JJfdA).

For example, when the thermoplastic resin A is polyethylene terephthalate, the thermoplastic phase hEJ that can be used is polyethylene terephthalate copolymerized with adipic acid, succinic acid, oxalic acid, glutaric acid, azelaic acid, sebacic acid, etc.
Polyesters obtained from aliphatic dicarboxylic acids and arbitrary glycols, or polyethers such as polyethylene glycol and polypropylene glycol are preferably used.

In addition, thermoplastic resin A is nylon 6 or nylon 6.6.
In this case, low molecular weight nylon or polyether such as polyethylene glycol having a melting point 20° C. or more lower than that of nylon can be used.

Furthermore, when the thermoplastic phase J]11A) is polycarbonate, polyethylene, polypropylene, etc., low molecular weight polymers thereof, waxes, polyethers, etc. can be used.

These thermoplastic phases JIIB) may be used alone,
Also, two or more types may be used in combination.

The thermoplastic resin (B) used can be in any form such as liquid, powder, granules, or lumps.

In addition, the thermoplastic resin Q has a melting point of thermoplastic resin ti
It may be lower or higher than A), but it is preferably one that is compatible with the thermoplastic resin A).

If this compatibility is poor, the additives blended into the thermoplastic phase J]mC) tend to be difficult to disperse uniformly in the resulting molded product, and the physical properties of the molded product also tend to become non-uniform.

Preferred examples of this thermoplastic phase Mho include those that are the same as the thermoplastic resin ~ or those shown above as examples of the thermoplastic phase J]mB).

In the present invention, the thermoplastic phase JIIB) is first deposited on the surface of the thermoplastic phase Q&A) at a temperature above the melting point of the thermoplastic phase fJMBJ and at a temperature below the melting point of the thermoplastic resin A.

To obtain the required temperature, heat may be applied to the mixing system from the outside, or stirring may be performed using a high-speed stirrer (for example, Yoda Seisakusho's Super Mixer or Miike Toatsu Kagaku's Henschel type mixer). The temperature may be raised by heat.

Moreover, both may be used together.

In such a temperature range, the thermoplastic resin (B) melts and adheres to the thermoplastic resin in a very short time.

On the other hand, the thermoplastic resin (A) is not melted and its quality is not impaired.

If the amount of thermoplastic resin (B) used is too small, it will not be effective in improving the dispersion of additives in the final molded product, and if it is too large, the physical properties of the molded product will be greatly reduced. Become.

The amount used is usually 0.0 mA) per thermoplastic phase J]1 mA).
001 to 0.1 times by weight, preferably O, OO5 to 0.0
It is 3 times the weight.

In the present invention, the thermoplastic resin N to which the thermoplastic phase BB has been adhered as described above is mixed with a powder of the thermoplastic resin q containing additive powder, and then molded according to a conventional method.

This mixing can be carried out by any method, such as a rotary mixer, a mixer with a stirring device (for example, manufactured by Nauta Mixer Wire Iron Works), or a high-speed stirrer.

If the additive is mixed alone with the thermoplastic resin (4) attached to the surface of the thermoplastic resin layer and molded, it will not work unless the additive has good compatibility with the thermoplastic resin B'fKA. cannot be highly dispersed.

However, if the additive is blended in advance with the thermoplastic phase JImQ as in the present invention, the additive and resin N
It can be highly dispersed regardless of whether it is compatible with or not.

Any method can be used to blend the additive into the thermoplastic resin (q), but a method in which it is sufficiently dispersed is preferable. with an amplitude of 3 mm or more and a frequency of 9c, p, s
The method of kneading additives by kneading with the above-mentioned vibrating mill (for example, commercially available vibration mill, vibro mill, etc.) involves adding the additives in advance during the synthesis reaction of Kizuki Umaq and cooling the resulting product. Melt the resin (q), add the additives, knead and disperse the additives into the resin (q) using a panburi mixer, roll mixer, etc., and then cool it to make it into a powder. There are methods etc.

The amount of additives to be added to the thermoplastic resin q can vary widely depending on the type of additive, the properties of the intended molded product, etc., but it is usually selected as appropriate from a range where the additive concentration is 3 to 90% by weight. Furthermore, the amount of thermoplastic resin q blended with this additive is 0.001~
It is preferable that the amount is 0.5 times by weight, particularly 0.01 to 0.1 times by weight.

The additives used in the present invention are those used as additives for thermoplastic resins, such as titanium oxide, zinc white, cadmium yellow, yellow lead, titanium yellow, ultramarine blue, iron oxide, carbon black, phthalocyanine green, phthalocyanine yellow, etc. inorganic and organic pigments; flame retardants such as perchloropentacyclodecane, tetrabrominated phthalic anhydride, hexafrombenzene, antimony trioxide, magnesium carbonate, and calcium salt carbonate; antistatic agents such as fatty acid esters of polyhydric alcohols; , silica, and other lubricants, and natural fibers and regenerated fibers such as cellulose and acetate can also be used.

The present invention will be described in detail below with reference to Examples.

Note that parts in the examples mean parts by weight.

0] of polyester at 35°C in oron chlorophenol.
This is the intrinsic viscosity determined from the value measured in .

Example 1 (A) (@0.630, single yarn denier 3 polyethylene terephthalate fiber was dried with a cutting machine to a drying length of about 1
Polyethylene terephthalate powder obtained by cutting into mm pieces 6
0 parts and 40 parts of phthalocyanine green fine powder were mixed, and hard chromium steel with a diameter of 20 mm was used as the grinding medium, the amplitude was 8 mm, the rotation speed was 120 Or, p;
, p, s) for 5 hours.

(B) Pellets of polyethylene terephthalate with a melting point of 263°C and □□□0.648 (4 x 4 mm x 2 mm)
') 1 part of a copolymerized polyester in which 40% of the terephthalic acid component of POIJ ethylene terephthalate having a melting point of 120°C was replaced with a succinic acid component was added to 100 parts,
Super mixer with a saturated steam steam jacket with a pressure of 3 kg/crA (rotary blade tip peripheral speed 20 m/crA)
See) for 5 minutes at 150°C.

The added copolymer was completely melted and adhered to the surface of the polyethylene pellets.

Next, the phthalocyanine green pigment 40 obtained in the above N
3 parts of dispersed polyethylene terephthalate powder were added and mixed for an additional 2 minutes in a supermixer.

The polyethylene terephthalate powder in which the pigment was dispersed was completely adhered to the surface of the polyethylene terephthalate pellet.

Next, this composition was melt-spun at 285°C and 150 de/
30 fil of filament yarn was obtained.

The obtained filament had a [η) of 0.635 and had a beautiful green color without inclusions.

Comparative Example 1 100 parts of polyethylene terephthalate used in Example 1, 1 part of the copolymer, and 3 parts of polyethylene terephthalate powder in which a pigment was dispersed were simultaneously mixed for 5 minutes using the super mixer used in Example 1.

In the resulting mixture, polyethylene terephthalate powder containing phthalocyanine green pigment was present in the form of lumps with a diameter of 2 to 50 mm.

Using this composition, filaments were spun by melt spinning in the same manner as in Example 1, but embedding was clearly observed in the filaments obtained, and the commercial value was extremely low.

Comparative Example 2 All samples were treated with a super mixer in the same manner as in Example 1, except that 1.2 parts of phthalocyanine green pigment was used instead of 3 parts of polyethylene terephthalate powder in which 40% phthalocyanine green pigment was dispersed. An attempt was made to obtain filaments of 150 deI/30 fil by melt spinning, but it was impossible to perform E-filtration in the spinning pack and spinning was impossible.

Example 2 (4) 100 parts of the same polyethylene terephthalate pellets as in Example 1 were added with an average molecular weight of 4 having a melting point of 56°C.
Add 0.5 part of 000 polyethylene glycol and add 10
The mixture was mixed for 10 minutes using a Nauta mixer kept at 0°C.

Polyethylene glycol completely adhered to the surface of polyethylene terephthalate pellets.

(B) Next, 4 parts of polyethylene terephthalate powder in which 50% iron oxide pigment was dispersed was added under the same conditions as in Example 1-(A), mixed for 30 minutes using a V-type mixer, and immediately heated to 285°C. Melt spinning 150 de'/3
A filament yarn of 0 fil was produced.

The obtained filament had an ω' value of 10.630, had no inclusions, and had a beautiful brown color.

Example 3 60 parts of copolyester powder in which 40% of the terephthalic acid component of polyethylene terephthalate having a melting point of 120°C was replaced with a cono-phosphoric acid component and carbon black 4
0 parts were mixed and processed in a vibrating mill under the same conditions as in Example 1-(4).

Next, 4 parts of the copolymerized polyester powder in which the above carbon black was dispersed was added to the polyethylene terephthalate pellets obtained in the same manner as in Example 2-(A) with polyethylene glycol adhered to the surface, and the mixture was further heated in a super mixer for 2 minutes. Mixed.

The copolyester powder in which carbon black was dispersed was completely adhered to the surface of the polyethylene terephthalate pellets.

Next, when this pellet was melt-spun at 285°C, the spinning could be carried out smoothly without any draughts, and the obtained filament was colored black, and [η] was 0.
．． It was 57.

Comparative Example 3 [η, 10.648 polyethylene terephthalate pellets (4miX4mmX2mm) 100 parts, melting point 5
A mixture of 0.5 parts of polyethylene glycol powder having an average molecular weight of 4000 and 1.6 parts of carbon black fine powder having a temperature of 6°C was mixed for 12 minutes using a super mixer, and then melt-spun in the same manner as in Example 3. One pass was not possible and spinning could not be completed.

Claims (1)

[Claims] 1. A thermoplastic resin (B) having a lower melting point than the thermoplastic phase J]i#A) was melted and adhered to the surface of the granular thermoplastic phase M'dAJ at a temperature below its melting point, and then additives were blended. A method for producing an additive-containing thermoplastic resin molded article, which comprises mixing powder of a thermoplastic resin (C) and then molding.