KR100575115B1 - Surface modified molding material comprising polyolefin and chlorinated polypropylene - Google Patents

Abstract

The present invention relates to a surface modifier of a polypropylene and chlorinated polypropylene blend, and a method for producing the blend, wherein the surface-modified polyolefin molding according to the present invention is a blend comprising 100 parts by weight of polyolefin and 1 to 60 parts by weight of chlorinated polypropylene. Characterized in that it is prepared by denaturing the moldings produced from primary or secondary amine modifiers.

In addition, the method for producing a surface-modified polyolefin molding of the present invention comprises the steps of mixing and pelletizing a mixture comprising chlorinated polypropylene and polyolefin; Forming a pellet to prepare a molding; And contacting the molding with an amine-based modifier.

Polypropylene, Chlorinated Polypropylene, Fiber, Amination, Modified, Modified, Dyeable

Description

Surface Modified Molding Material comprising polyolefin and chlorinated polypropylene}

The present invention provides a method for reforming a polypropylene containing chlorinated polypropylene (CPP) and a modifier produced by the method for reforming the polypropylene. It is to provide a novel surface modified polypropylene that can improve the printability by increasing the adhesion of the ink during printing, coating.

Polyolefins including polypropylene, especially polypropylene, have high melting points and are excellent in strength and chemical resistance because they are crystalline high molecular materials. In addition, it is light, strong and wear-resistant properties when molded into a fiber, as well as low cost compared to polyester, nylon, etc. are used in a variety of clothing and industrial materials.

However, polypropylene has a poor affinity with moisture as a non-polar group, so that the ink is inferior in printability in ink using a medium having a polar group such as acrylic in both water-soluble ink and oil-soluble ink, so that dyeing or printing Due to the inferior characteristics, the use thereof is restricted.

Printability, such as dyeability and printing, is judged as the wetness index, but as is known, the wetness index of plastics is low. In particular, polypropylene has a very low wetness index, which prevents various surface treatments such as printing. In order to solve this problem and increase the wetness index, it is common to perform a corona discharge treatment. However, the wetness index of the forcibly raised plastic surface decreases over time.

Fibers made of polypropylene-based resins such as propylene homopolymers or propylene-based propylene or α-olefin copolymers, which have been conventionally used, also have poor printability, and at high temperatures even when the wetness index is increased by corona treatment. When left for a long time, the wetness index is significantly lowered and cannot be used for printing purposes.

In the case of a film made of homo polypropylene, the surface tension of the biaxially stretched film and the unstretched film is 33 to 34 dynes / cm, and the surface tension is 40 to 45 dynes / cm when the corona treatment is performed to improve printability. However, due to the influence of external environment such as heat, especially in summer, the surface tension of the film decreases rapidly with time, and workability such as printing and deposition is significantly reduced.

In order to solve the above problems, a method of blending a polypropylene resin or introducing a polar group through graft polymerization has been studied. However, due to the complexity of the fundamental polymerization process, it is not widely commercialized and the graft efficiency of the polar monomer is poor. It does not secure adhesiveness and printability.

The inventors have conducted various studies to solve the above problems, and as a result of blending and spinning with CPP and polypropylene or other polyolefins, the polyolefin fibers modified with amine compounds give a wide range of properties and have various printability and adhesive properties. It has been found to give excellent properties to complete the present invention.

In addition, the present invention has completed the present invention which imparts excellent properties in printability and ink adhesion by modifying the surface of a molding comprising a sheet of polyolefin containing CPP.

Accordingly, the present invention mixes and blends polychlorinated chlorinated polypropylene which is well mixed with polyolefin and can easily introduce a polar group while imparting heat resistance, followed by spinning and modifying the surface of the spun fiber, or blending the blend with a sheet or the like. The molded molding is modified to provide a polyolefin fiber or molding having improved printability.

     That is, the present invention provides a sheet, a nonwoven fabric and a fabric produced by modifying the surface of a molded article, such as a sheet made of a blend of polypropylene and chlorinated polypropylene, and a nonwoven fabric, fabric, etc., formed using fibers made of the same blend. Various moldings, such as these are provided.

It is still another object of the present invention to provide a novel polyolefin molding having improved printability and a manufacturing method for modifying the surface of various molded articles prepared from the molding.

The polypropylene modifier is a mixture of polypropylene and chlorine content of 1 to 45% by weight, and chlorinated polypropylene having a molecular weight of 1000 to 400,000 to spun to form a fiber or to form a molded article of the blend into a sheet or the like. It is prepared by reforming by adding to a reforming reaction solution containing.

The production method according to the present invention comprises the steps of preparing a fiber or a fabric using the fiber by kneading and spinning chlorinated polypropylene and polyolefin, or a molded article such as a sheet using a blend of the CPP and polypropylene;

Adding a molded article of the prepared fiber, fabric or sheet to a reaction solution to reformate the reaction solution;

Washing the modified fibers, fabrics or shaped bodies with water;

It provides a method for producing a modified polypropylene, characterized in that it comprises a modified polyolefin fiber produced by the method and a modified polyolefin fabric using the fiber.

Although the physical properties of the chlorinated polypropylene used in the present invention are largely limited, those having a molecular weight of 1,000 to 400,000 and a chlorine content of 1 to 45% by weight are used.

As the main component used in the present invention, the use of polypropylene is most preferred because of its compatibility with chlorinated polypropylene, but polyolefins compatible with conventional chlorinated polypropylene such as polyethylene, propylene and ethylene or other alpha Copolymers of olefins, copolymers of ethylene and alpha olefins, and the like can be used.

The ratio of the polypropylene or polyolefin according to the present invention and the chlorinated polypropylene may be selected and used by those skilled in the art as needed. Usually, 1 to 60 parts by weight of chlorinated polyolefin may be used with respect to 100 parts by weight of polyolefin. 45 parts by weight is recommended. If it is 1 part by weight or less, the effect is insufficient for the subsequent dyeing improvement, and when it is 60 parts by weight or more, the physical properties of the produced fibers do not appear.

As a reforming reactant for modifying the chlorinated polypropylene fiber, an amine group is substituted by a chlorine substitution reaction by reacting with an amine compound having at least one primary or secondary amine group to produce an amine-modified chlorinated polypropylene. The modifier causes a substitution reaction of the chlorine group in the main chain of the chlorinated polypropylene to have a structure in which the amine group depends on the main chain of the chlorinated polypropylene group, thus maximizing the polar group to improve printability and printing property.

The amine compound used as the modifying agent of the present reaction is a primary amine or a secondary amine, and any compound having or without a substituent may be used.

As the usable amine, the primary amine is the same as the compound of the following formula.

NH2-A1

     (In the above, A 1 is a hydrocarbon having 1 to 18 carbon atoms which is branched or includes a cyclic or aromatic ring, and includes one or more hetero functional groups selected from nitrogen, oxygen, and sulfur in the main chain or side chain.)

Primary amines of the above structural formula include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, iso Octylamine, aniline, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, aminopropanol, aminobutanol, benzidine, 4,4'-diaminobenzanilide, aminobenzenesulfonic acid, diaminobenzene, Aminopropanol, phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyloxide, 4,4'-diaminodicyclo Hexyl ether, 4,4'-diaminodiphenyl-3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, dimethylaminopropylamine and the like.

As the secondary amine of the present invention, a compound having the following structural formula is used.

A2-NH-A3

     (A2 and A3 are branched or hydrocarbons having 1 to 18 carbon atoms including cyclic or aromatic rings and include those having at least one functional group selected from nitrogen, oxygen, sulfur, etc. in the main or side chains.) Representative examples include dimethyldiamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, dicyclohexylamine, diheptyl Amine, dioctylamine, diisooctylamine, diphenylamine, methylaniline, ethylaniline, propylaniline, butylaniline, hydroxyethylaniline, hydroxypropylaniline, methylethanolamine, ethylethanolamine, diethanolamine, Dipropanolamine etc. are mentioned, for example.

As the secondary amine of the present invention, it is also possible to use the following amine compounds.

A4-HN- (A5-NH-A6-NH) n-A7

     (The A4 to A7 is a branched or hydrocarbon having 1 to 18 carbon atoms including cyclic or aromatic ring and includes one or more functional groups selected from nitrogen, oxygen, sulfur, etc. in the main chain or side chain, n is 1 It is a positive integer between ~ 10.)

Examples of the secondary amines include diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexaamine, polyethyleneimine, dicyandiamide, aminoethylethanolamine, and the like.

The modification reaction temperature of the present invention can be changed depending on the solvent and reactivity, but is not greatly limited, but is usually reacted in the range of 30 to 100 ° C. for 1 to 48 hours, preferably 3 to 30 hours.

The modified polymer according to the present invention may additionally have surface properties depending on the structure of the amine compound being modified.

The modified polyolefin fibers or fabrics produced by the present invention, unlike the existing polyolefin fibers and fabrics, may have excellent printability and physical properties such as additional antioxidants and antistatic agents, depending on the modified modifiers, and thus their functions are further enhanced. Doubling

Hereinafter, the present invention will be described in more detail through examples of the reforming reaction of polyolefin fibers or fabrics containing chlorinated polypropylene according to the present invention. This embodiment is only shown as one embodiment of the present invention, the present invention is not limited by the following examples, those skilled in the art can understand the present invention through the detailed description of the above description.

Example 1

     90 parts by weight of polypropylene (Hyundai Petrochemical, 7620) and 10 parts by weight of chlorinated polypropylene (Toyo Kasei 13-LP) were adjusted to the temperature of the screw (210 ° C, 220 ° C, 220 ° C, 210 ° C). Masterbatch was prepared using an extruder of Sewon M-Teck having a single screw. The prepared pellets were placed in a raw material hopper of a melt spinning machine, transferred to a feed part of an extruder by rotating a screw, and melted and mixed, and spun multifilaments made of 90 thread strands to a thickness of 10 denier. The temperature of the spinning machine was maintained at 210 ~ 230 ℃ spinning. Spinning pressure was maintained at 100 ~ 300kg / ㎠, in order to obtain a uniform extrusion amount during melt spinning was equipped with a gear pump to make a constant spinning pressure. The melt spun fiber was cooled to room temperature to obtain a fiber.

10 g of the obtained 10 denier fibers were added to 100 g of diethylenetriamine, and then reacted at 85 ° C. for 1 day in a nitrogen atmosphere. After cooling, the fiber was repeatedly washed five times with distilled water, dehydrated in a centrifuge, and dried to obtain a surface treated fiber.

Example 2

Except for using 95 parts by weight of polypropylene and 5 parts by weight of chlorinated polypropylene in Example 1 was carried out in the same manner as in Example 1 to obtain a surface-treated fibers.

Example 3

      Except that 10g of fibers in Example 1 was added to the mixed solvent consisting of 50g of diethylenetriamine and 50g of water was reacted in the same process.

Example 4

      Except that 10g of the fiber in Example 2 was added to the mixed solvent consisting of 50g of diethylenetriamine and 50g of water was reacted in the same process.

Comparative Example 1

      Fibers were prepared under the same conditions except that surface treatment was not performed in Example 1.

Comparative Example 2

      Fibers were prepared under the same conditions except that surface treatment was not performed in Example 2.

Comparative Example 3

      The fiber was manufactured under the same conditions as in Example 1 except that the fiber was prepared by spinning with polypropylene alone in Example 1.

Dyeability Evaluation

      0.013 parts by weight (0.013% owf) of Lumacron Yellow E3G 200% dye in distilled water, 0.3 parts by weight (0.3% owf) of Paianil Red FD-BDY 200% dye, 1.7 parts by weight of Dianix Blue FBLE 100% dye (1.7% owf) After adjusting the pH to 4 to 4.5 with glacial acetic acid, 0.3 part (0.3% owf) of a dispersant (Sunsolt RM-340) was added to prepare a salt bath of 3000 parts.

After dyeing the fiber prepared according to the above example in a salt bath at 30 ° C. for 30 minutes at 130 ° C. and 20 minutes at 130 ° C. in a Mathis dyeing machine, the dye was washed with distilled water at 80 ° C. The dyeings were reduced in water at 80 ° C. for 20 minutes in a bath containing 1 g / l caustic soda and 2 g / l NaHSO ₃ (sodium hydrosulfite) and washed with water to obtain a dyed yarn. The results of measuring the color density of the dyed yarn with a colorimeter (Data Color) are shown in Table 1.

[Table 1] Color Concentration of Surface Treated Fiber

As shown in Table 1, the fiber treated with diethylenetriamine was remarkably excellent in dyeing as compared to the untreated fiber.

Example 5

     A sheet was prepared by pressing 10 g of the masterbatch prepared in the same manner as in Example 1 between hot plates heated to 220 ° C. in a hydraulic press for 10 seconds. The obtained sheet was put in 100 g of diethylenetriamine, and then reacted at 85 ° C. for 1 day in a nitrogen atmosphere. After cooling, the sheet was repeatedly washed five times with distilled water and dried to obtain a sheet having a surface treatment. In order to evaluate the dyeability, the experiment was conducted under the same conditions using the same dye bath performed in the dyeing test.

[Comparative Example 4]

10 g of the pressed sheet as in Example 5 was tested under the same conditions using the same dye bath performed in the dyeing test for dyeability evaluation without surface treatment of the diethylenetriamine in Example 5. It was found that the surface modification was significantly inferior to that of.

It was found that the polyolefin molding prepared by molding the mixed resin of chlorinated polypropylene and polyolefin of the present invention can be produced simply and effectively with a modified molding substituted with chlorine by an amine compound, and the modified modified molding may be dyed and printed. It was found that this was greatly increased. In addition, by selecting the structure of the modified amine compound, according to the functional group of the amine compound, by using an amine compound having various functions such as UV protection function, antistatic function and antioxidant function group as a modifier, the ultraviolet light as the modified modified molding itself It is expected to have various functions such as prevention function, oxidation prevention function, flame retardant function and antistatic function.

Claims (16)

A surface modified polyolefin molding produced by modifying a molding made from a blend comprising 100 parts by weight of polyolefin and 1 to 60 parts by weight of chlorinated polypropylene with a primary amine or secondary amine modifier.       The method of claim 1,      The amine compound is a modified polyolefin molding, characterized in that the primary amine compound of the formula 1.       [Formula 1] A1-NH2      (In the above, A 1 is a hydrocarbon having 1 to 18 carbon atoms which is branched or includes a cyclic or aromatic ring, and includes one or more hetero functional groups selected from nitrogen, oxygen, and sulfur in the main chain or side chain.)       The method of claim 2,      The amine compound may be methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, isooctylamine, Aniline, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, aminopropanol, aminobutanol, benzidine, 4,4'-diaminobenzanilide, aminobenzenesulfonic acid, diaminobenzene, aminopropanol , Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyloxide, 4,4'-diaminodicyclohexyl ether And at least one compound selected from 4,4'-diaminodiphenyl-3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, and dimethylaminopropylamine. Polyolefin moldings.        The method of claim 1,      The amine compound is a modified polyolefin molding, characterized in that the secondary amine compound of the formula 1.       [Formula 1] A2-NH-A3      (In the above, A2 and A3 are branched or hydrocarbons having 1 to 18 carbon atoms including cyclic or aromatic rings, and include those having at least one hetero functional group selected from nitrogen, oxygen, and sulfur in the main chain or side chain. )       The method of claim 4, wherein the amine compound is dimethyldiamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, Dicyclohexylamine, diheptylamine, dioctylamine, diisooctylamine, diphenylamine, methylaniline, ethylaniline, propylaniline, butylaniline, hydroxyethylaniline, hydroxypropylaniline, methylethanolamine, ethylethanol A modified polyolefin molded article, characterized in that at least one compound selected from amine, diethanolamine, dipropanolamine.       The method of claim 1,      The amine compound is a modified polyolefin molding, characterized in that the secondary amine compound of the formula 1.      A4-HN- (A5-NH-A6-NH) n-A7      (The A4 to A7 is a branched or hydrocarbon having 1 to 18 carbon atoms including cyclic or aromatic ring and includes one or more functional groups selected from nitrogen, oxygen, sulfur, etc. in the main chain or side chain, n is 1 It is a positive integer between ~ 10.)       The method of claim 6,      The amine compound is a modified polyolefin molding, characterized in that any one or more compounds selected from diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexaamine, polyethyleneimine, dicyandiamide, aminoethylethanol amine .       The method according to any one of claims 1 to 7, wherein The molding is a modified polyolefin molding, characterized in that the fiber, fabric, non-woven fabric, sheet.       Mixing and pelletizing a mixture comprising chlorinated polypropylene and polyolefin;       Forming a pellet to prepare a molding;       Modifying the molding by contact with an amine-based modifier;       A method for producing any one of the surface-modified polyolefin moldings selected from claims 1 to 7 comprising a.        The method of claim 8,       Wherein said polyolefin is a copolymer of polyethylene, ethylene-alpha olefin, propylene polymer, copolymer of propylene and alpha olepan.       The method of claim 10,      The amine compound is a method for producing a modified polyolefin molding, characterized in that the primary amine compound of the formula 1.       [Formula 1] A1-NH2      (In the above, A 1 is a hydrocarbon having 1 to 18 carbon atoms which is branched or includes a cyclic or aromatic ring, and includes one or more hetero functional groups selected from nitrogen, oxygen, and sulfur in the main chain or side chain.)       The method of claim 11,      The amine compound may be methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, isooctylamine, Aniline, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, aminopropanol, aminobutanol, benzidine, 4,4'-diaminobenzanilide, aminobenzenesulfonic acid, diaminobenzene, aminopropanol, Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyloxide, 4,4'-diaminodicyclohexyl ether, Modified polyolefin, characterized in that any one or more compounds selected from 4,4'-diaminodiphenyl-3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, dimethylaminopropylamine Manufacturing moldings Way.       The method of claim 10,      The amine compound is a method for producing a modified polyolefin molding, characterized in that the secondary amine compound of the formula 1.       [Formula 1] A2-NH-A3      (In the above, A2 and A3 are branched or hydrocarbons having 1 to 18 carbon atoms including cyclic or aromatic rings, and include those having at least one hetero functional group selected from nitrogen, oxygen and sulfur in the main chain or side chain. )       The method of claim 13, wherein the amine compound is dimethyldiamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, Dicyclohexylamine, diheptylamine, dioctylamine, diisooctylamine, diphenylamine, methylaniline, ethylaniline, propylaniline, butylaniline, hydroxyethylaniline, hydroxypropylaniline, methylethanolamine, ethylethanol A process for producing a modified polyolefin molding, characterized in that at least one compound selected from amines, diethanolamines, dipropanolamines.       The method of claim 10,      The amine compound is a method for producing a modified polyolefin molding, characterized in that the secondary amine compound of the formula 1.      A4-HN- (A5-NH-A6-NH) n-A7      (The A4 to A7 is a branched or hydrocarbon having 1 to 18 carbon atoms including cyclic or aromatic ring and includes one or more functional groups selected from nitrogen, oxygen, sulfur, etc. in the main chain or side chain, n is 1 It is a positive integer between ~ 10.)        The method of claim 15, The amine compound is a modified polyolefin molding, characterized in that any one or more compounds selected from diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexaamine, polyethyleneimine, dicyandiamide, aminoethylethanolamine How to prepare.