KR19990084658A - Functional polypropylene resin composition to which a functional substance is added and its manufacturing method - Google Patents

Abstract

The present invention relates to a method for preparing a functional polypropylene resin composition to which a functional material is added, and in particular, it is possible to dye fibers, films, moldings and dyes by providing dyeing, adsorption, adhesiveness, and affinity that did not exist in conventional polypropylene resins. It can be used in various industrial fields.

In order to achieve the above object, the present invention is to uniformly disperse 1 part to 20 parts of semicrystalline functional polymer, 0.5 parts to 5 parts of amorphous functional polymer and 0.1 parts to 5 parts of low molecular weight additive in a weight ratio of 100 parts of polypropylene. .

Description

Functional polypropylene resin composition to which a functional material is added and its manufacturing method

The present invention relates to a functional polypropylene resin composition which is easily molded and colored by allowing a mixture of semi-crystalline polymers and amorphous polymers to be formed in polypropylene, which is a crystalline polymer. The present invention relates to a novel functional polypropylene resin composition which significantly improves the dye adsorption of disperse dyes by allowing the paper-like polymolecular substance to be uniformly dispersed and incorporated into polypropylene.

Polypropylene is a crystalline polymer having no polar group, as shown in the formula (1), and has excellent processability, physical properties, and mechanical properties to be used as a raw material for products commonly used such as fibers, films, and plastics. In contrast, polypropylene is composed of only carbon and hydrogen atoms and does not have a polar group capable of imparting chemical properties. Thus, polypropylene exhibits a property of inferior chemical function such as affinity, adsorption, adhesiveness, and dyeability. In particular, it is impossible to give polypropylene a color after molding.

It is possible to give a color through the dyeing process to adsorb and fix dye, but since polypropylene has no dyeing seat which can have affinity with dye, conventional dyeing method is to give color to polypropylene molded products. impossible.

Therefore, in the present invention, in order to widely use polypropylene as a raw material for everyday life products that require various colors, a novel polymer that provides new functions such as dyeability, adsorption, affinity, adhesiveness by uniformly dispersing and mixing functional polymer materials in polypropylene. It is to provide a functional polypropylene resin composition. In addition, in order to uniformly disperse and mix functional polymer materials in polypropylene, a new polypropylene resin composition in which polypropylene and functional polymer are effectively mixed by mixing together semicrystalline functional polymer and amorphous functional polymer together in crystalline polypropylene. .

As an example of mixing a polymer material with polypropylene, Sung-il Hong et al. (J. Soc. Dyers Color, vol 110 (1), p19-23, 1994) used a stearyl methacrylate copolymer polymer to improve the dyeability of polypropylene. Polypropylene may be mixed with polypropylene, and Wilbuts D. J et al. (PCT Int. Appl. 9409067 A1, April 28, 1994) functionalized with anhydrides, carboxylates, acrylates, etc. In some cases, Seves A. et al. (Dyes Pigm., Vol. 28 (1) p 19-29, 1995) have mixed oligocyclopentadiene with polypropylene.

In addition, in order to impart color to the polypropylene, it is common to add and mix particulate pigments in the polypropylene melt as Laverty K. J. (Brit. UK Pat. Appl. 2242390, October 2, 1991). Hishida I. (Eur. Pat. Appl. 625538 A1, Nov. 23, 1994) produces colored thermoplastic chips by mixing powdered pigments with polypropylene together with thermoplastic polymer additives.

In the existing technology as described above, it is possible to give a dyeable function by adding and dispersing a polymer material capable of providing an adsorption seat of a dye to polypropylene, but a single polymer or a simple mixed polymer in which the additive polymer used is extremely limited is used. Therefore, it is difficult to produce practically. In addition, it was attempted to impart a dyeability or functionality to the polypropylene by simply mixing with an additive polymer or powdery dye, and did not consider the practicality and structural characteristics of the composition at all.

In the present invention, attention has been paid to the fact that polypropylene is crystalline, and has been reported so far to have a mixture of semi-crystalline polymers and amorphous polymers in polypropylene, which have uniformly dispersed structural properties and are easily colored by a general coloring method. It is an object of the present invention to provide a novel functional polypropylene resin composition.

In the polypropylene resin composition of the present invention, the polymer produced and supplied is generally added to the polypropylene, but the polypropylene resin composition is provided with functions such as dyeability and adsorption without impairing the inherent properties of the polypropylene. This is because the mixing of crystalline, semi-crystalline and amorphous polymers, which are possible only in the case of, have structural properties.

The present invention relates to a polypropylene that can be colored by a dyeing method formed by uniformly dispersing and mixing 1 part to 20 parts of semi-crystalline polymers, 0.5 parts to 5 parts of amorphous polymers and 0.1 parts to 5 parts of low molecular weight additives in 100 parts by weight of polypropylene. The present invention relates to a propylene resin composition and a method of manufacturing the same.

According to the present invention, the polypropylene is isotactic, having a weight average molecular weight of 10,000 to 1,000,000, and a molten resin of 1dg / min. To 100 dg / min.

Semi-crystalline functional polymers are polymers that form incomplete crystals between crystalline polymers and amorphous functional polymers. Ethyl vinyl acetate copolymers such as Structural Formula (2) having a function of adsorbing dyes are used, and polyvinyl alcohol copolymers, Acrylic copolymers, polyester copolymers, polyamide copolymers and the like can be used.

Ethylene vinyl acetate copolymer has a vinyl acetate content of 10% to 50% by weight and a melt index of 1 dg / min. To 400dg / min. By ASTM D-1238 test method, and the vinyl acetate content is 20 by weight. % To 40% and melt index 10 dg / min. To 100 dg / min. It is more preferable that is.

The amorphous functional polymer uses a polyhydroxyether polymer having a hydroxyl group, an ether group and an aromatic group for imparting affinity between the semicrystalline functional polymer and polypropylene as an amorphous polymer that does not form crystals.

The amorphous functional polymer is a polyhydroxyether thermoplastic polymer prepared by reacting an aromatic diol and epichlorohydrin in an equivalent ratio, and has a linear molecular structure as shown in the formula (3), and has a weight average molecular weight between 1,000 and 100,000. In addition, epoxy resins, novolak-type phenol-formaldehyde resins and the like can be used.

Aromatic diols include 4,4'-isopropylidenediphenol, 4,4'-isopropylidenedi (3,5-dimethyl) phenol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl, 4 , 4'-dimethylenediphenol, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide and the like can be used. . In addition, the novolak-type phenol-formaldehyde resin is prepared by reacting phenol and formaldehyde under an acidic catalyst, and a softening point of 50 ° C. to 150 ° C. may be used.

In addition, the low molecular weight additive may be used as a material added to impart the chemical, thermal, optical and physical stability of the polypropylene thermal stabilizer, light stabilizer, UV stabilizer, flame retardant, softener, wetting agent, plasticizer, antistatic agent and the like.

The polypropylene resin composition of the present invention has a dual function by adding polyhydroxy ether, which is an amorphous functional polymer, as a third component in the process of incorporating crystalline polypropylene as a main component and adding an ethyl vinyl acetate copolymer which is a semi-crystalline functional polymer. It not only achieves uniform dispersion of the polymer but also maximizes the functions of affinity, adsorption, adhesion and dyeing.

The polypropylene resin composition of the present invention is a multicomponent material of polypropylene-ethyl vinyl acetate copolymer-polyhydroxy ether, which has not existed until now, and is mixed with crystalline-quasi-crystalline-amorphous polymers in a single resin composition. It consists of:

Polypropylene resin composition of the present invention has a tensile strength (ASTM D638) of 200kg / cm ² to 500kg / cm ² Flexural modulus (ASTM D790) is 10,000kg / cm ² ~ 20,000kg / cm ^{2 And} softening point (ASTM D1525) Have physical properties of 140 ° C to 160 ° C. In addition, the adsorption and diffusion rate of the disperse dyes significantly increase, and the affinity, adsorption, etc. are improved.

As shown in Fig. 1, the polypropylene resin composition of the present invention shows a significant increase in the adsorption of the disperse dyes and the internal diffusion of the adsorbed dyes, when compared with pure polypropylene.

Put the polypropylene resin composition chip and the pure polypropylene chip of the present invention in the dyeing machine at the same time in a dye bath of disperse dyes (CI Disrerse Red 60, CI Disperse Yellow 42 and Disperse Blue 165) at high temperature and high pressure (high temperature 130 ℃, pressure 1 atm to 4 atm) and heat-dyed for 30 to 60 minutes. In the functional polypropylene resin composition of the present invention, as shown in Figure 1, the disperse dye penetrates during the dyeing process, the polypropylene resin composition of the present invention has the adsorptivity and permeability of the disperse dyes that could not be found in pure polypropylene And dyeing amount are between 2.0 * 10 <^-4> mol / g and 15 * 10 <^-4> mol / g.

Polypropylene resin composition of the present invention by dropping 0.5 μm droplets on the surface of the resin composition in the form of a film to measure the contact angle between the droplet and the surface of the resin composition exhibits a phenomenon that the contact angle is significantly reduced to 3 to 30 degrees, pure polypropylene Compared to the other, the hydrophilicity is excellent.

The polypropylene resin composition of the present invention exhibits dyeing, adsorption, absorbency, adhesion, and affinity that did not exist in the existing polypropylene resin, and thus can be used to prepare dyeable fibers, easy printing films, and moldings of various colors. Can be.

1: Dyeing state diagram of the functional polypropylene resin composition chip dyed with disperse dyes of the present invention

2: Dyeing state diagram of the conventional polypropylene chip dyed with a disperse dye

<Description of the symbols for the main parts of the drawings>

Hereinafter, an embodiment of the present invention will be described in detail.

(Examples below are illustrative of the limited case to more specifically describe the contents of the present invention, but the scope of the present invention is not limited thereto.)

Example 1

In a mixer (WARNER & PELEIDERER Type ZSK25) put 0.05 kg of polyhydroxy ether (PAPHEN Phenoxy Resin) and 0.35 kg of ethyl vinyl acetate copolymer (EVAFLEX 260) in 4.65 kg of isotactic polypropylene having a melt index of 25 dg / min. The resin composition was prepared by mixing in a compounder at a screw speed of 250 rpm and a mixing amount of 15 kg / h at an hour.

The polypropylene resin composition prepared above is a mixture of polypropylene, ethyl vinyl acetate copolymer and polyhydroxy ether, which is composed of polypropylene as a substrate, and has a structure in which ethyl vinyl acetate copolymer is well dispersed and incorporated in polypropylene. Polyhydroxyethers have been shown to be well mixed in polypropylene and ultra fine units, improving the affinity of polypropylene.

The polypropylene resin composition in the chip state was dyed at 130 ° C. for 60 minutes with a disperse dye (CIDisperse Red 60) to have a dyeing amount of 6.7 × 10 ⁻⁴ mol / g.

Example 2.

In a mixer (WARNER & PELEIDERER Type ZSK25), 0.05 kg of phenol-formaldehyde and 0.35 kg of ethyl vinyl acetate copolymer (EVAFLEX 260) were placed in 4.65 kg of isotactic polypropylene having a melt index of 25 dg / min., And the screw speed was 250 rpm. And it mixes with a compounder at a mixing amount of 15 kg / h per hour to prepare a resin composition.

The polypropylene resin composition prepared above is a mixture of polypropylene, ethyl vinyl acetate copolymer and polyhydroxy ether, which is composed of polypropylene as a substrate, and has a structure in which ethyl vinyl acetate copolymer is well dispersed and incorporated in polypropylene. Polyhydroxyethers have been shown to be well mixed in polypropylene and ultra fine units, improving the affinity of polypropylene.

When the polypropylene resin composition in the chip state was dyed at 130 ° C. for 60 minutes with a disperse dye (CIDisperse Red 60), it had a dyeing amount of 5.4 × 10 ⁻⁴ mol / g.

Example 3.

In a mixer (WARNER & PELEIDERER Type ZSK25), 0.05 kg of epoxy resin and 0.35 Kg of ethyl vinyl acetate copolymer (EVAFLEX 260) were placed in 4.65 kg of isotactic polypropylene having a melt index of 25 dg / min. A resin composition is prepared by mixing with a compounder at a mixing amount of 15 kg / h.

The polypropylene resin composition prepared above is a mixture of polypropylene, ethyl vinyl acetate copolymer and polyhydroxy ether, which is composed of polypropylene as a substrate, and has a structure in which ethyl vinyl acetate copolymer is well dispersed and incorporated in polypropylene. Polyhydroxyethers have been shown to be well mixed in polypropylene and ultra fine units, improving the affinity of polypropylene.

When the polypropylene resin composition in the chip state is dyed at 130 ° C. for 60 minutes with a triglyceride dye (CIDisperse Red 60), it has a dyeing amount of 5.7 × 10 ⁻⁴ mol / g.

Accordingly, the present invention provides a novel functional polypropylene resin composition in which two or more types of polymolecules having a polypropylene as a main component and having a polar group are uniformly dispersed and mixed in the polypropylene, thereby significantly improving the dye adsorption of the disperse dyes. It is possible to make a wide range of applications throughout the industry, such as making possible fibers, printable films and moldings of various colors.

Claims (4)

1 to 20 parts of semi-crystalline polymers, 0.5 to 5 parts of amorphous polymers and 0.1 to 5 parts of low molecular weight materials are uniformly dispersed and mixed in a weight ratio of 100 parts of polypropylene between 10,000 and 1,000,000. A functional polypropylene resin composition in which a functional substance having a dyeing property between 2.0 × 10 ⁻⁴ mol / g and 15 × 10 ⁻⁴ mol / g is added to the disperse dye so as to prepare the same. The method of claim 1, wherein the semi-crystalline functional polymer is an ethyl vinyl acetate copolymer, a polyvinyl alcohol copolymer, a polyacryl copolymer, a polyester copolymer, a polyamide copolymer and a polystyrene copolymer, and the amorphous functional polymer is a polyhydroxy ether , Epoxy resins and novolak-type phenol-formaldehyde resins, and low molecular weight additives are heat stabilizers, light stabilizers, flame retardants, softeners, wetting agents, plasticizers, antistatic agents, pigments, ultraviolet absorbers, characterized in that a mixture of two or more. Functional polypropylene resin composition to which a functional material is added. The method of claim 2, wherein the ethyl vinyl acetate copolymer has a vinyl acetate content of 10% to 50% by weight and a melt index of 1 dg / min. The polyhydroxy ether having a weight average molecular weight of 1,000 to 100,000 is a polyhydroxy ether having a weight average molecular weight of 400 to dg / min. 1 to 20 parts of semi-crystalline polymers, 0.5 to 5 parts of amorphous polymers and 0.1 to 5 parts of low molecular weight materials are uniformly dispersed and mixed in a weight ratio of 100 parts of polypropylene between 10,000 and 1,000,000. A method for producing a functional polypropylene resin composition in which a functional substance having a dyeability between 2.0 × 10 ⁻⁴ mol / g and 15 × 10 ⁻⁴ mol / g is added to a disperse dye so as to prepare the same.