JPS62162042A - Knitted fabric excellent in dyeability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a knitted fabric made of propylene copolymer fiber that has excellent dyeing properties. More specifically, the present invention relates to a knitted fabric made of propylene polymer fibers dyed by a piece dyeing method.

(b) Prior Art It is well known that polyolefins are difficult to dye, and considerable efforts have been made to solve this problem.

Generally, to improve the dyeability of polyolefins, a dye receptor is mixed therein.

These dye receptors include polyamides which are polycondensates of cyclic amides, polyamides which are polycondensates of aliphatic diamines and dicarboxylic acids, polyurethanes, polyureas, and polycondensates of alkylene glycols and dicarboxylic acids. polyesters, polyalkyleneimines containing from 2 to 20 carbon atoms and substances selected from the group consisting of chlorinated paraffin waxes, diisocyanates, lower fatty acid anhydrides, hydrohalic acids and -basic fatty acid chlorides. reaction products are used.

Such a dye acceptor can also be prepared by reacting an alkylene imine in which the alkylene group contains 2 to 20 carbon atoms with epichlorohydrin, 4°4'-dioxydiphenyldimethyl-methane, and monoethanolamine. A mixture of the resulting epoxy resin with the reaction product has been used. Furthermore, as dye acceptors thermoplastic polymers of vinyl substitutes and polycyclic pyridine bases,
Thermoplastic polyamides, including condensation homopolymers and copolymers containing or having appendage groups consisting of amide groups; condensation homopolymers and copolymers in which amine groups are a constituent part of the polymer chain; and amine groups are used and also include amine polymers and other basic nitrogen polymers, including addition homopolymers and copolymers having appendage groups consisting of amine groups, such as polyurethanes, polyureas, poly(vinyl carbazole) and aniline-formaldehyde resins have been used.

However, this method not only requires expensive materials, but also
The dyeability is still insufficient, and it is difficult to obtain durable dyed products, especially in piece dyeing, which involves dyeing after knitting and weaving.

(c) Problems to be solved by the invention The purpose of the present invention is to dye a propylene resin knitted fabric with excellent fiber properties such as heat resistance and abrasion resistance by piece dyeing to obtain a durable dyed product. do.

B) Summary of the Invention As a result of extensive research into improving the dyeing properties of polyolefins, the present inventors have found that certain comonomers with double bonds, specifically branched 1,4 dienes, exhibit excellent dyeing properties. The present invention was achieved by discovering that particularly excellent dyeing properties are exhibited within a certain range of branched 1,4 diene content.

More specifically, it consists of at least propylene and a branched 1,4 diene represented by formula (I), the content of the 1,4 diene is 0.01 to 30 mol%, and the melt index is 5 oar/1 o min or less. An object of the present invention is to provide a knitted fabric with excellent dyeing, which is produced by knitting and weaving a filament obtained from a propylene polymer resin containing an unsaturated copolymer resin, and then dyeing it.

(Here, R1 represents an alkyl group having 8 or less carbon atoms, and R2 and R3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms. However, R2 and R3 are not both hydrogen atoms.) (E) Specific Description Unsaturated Copolymer Resin (I) Composition The unsaturated copolymer resin used in the present invention consists of propylene and a branched 1,4-diene (hereinafter referred to as a branched 1,4-diene) represented by the formula (I). It is a copolymer consisting of α-olefin (excluding propylene) having 2 to 12 carbon atoms as required.

(Here, R1 represents an alkyl group having 8 or less carbon atoms, and t and R3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms. However, R2 and R3 are not both hydrogen atoms.) The branched 1,4-diene content of the polymer is 0.0
1 to 30 mol%, carbon number 2 to 1 excluding propylene
The α-olefin content of No. 2 is 0 to 20 mol%.

When the branched 1,4-diene content is less than 0.01 mol%,
If the amount exceeds 30 mol %, the polymerization rate will drop significantly, making it unsuitable for industrial production.

If the content of α-olefins having 2 to 12 carbon atoms (excluding propylene) exceeds 20 mol %, the elastic modulus decreases too much, which is beyond the scope of the present invention.

Moreover, it is undesirable because it causes a decrease in the polymerization rate and an increase in the amount of by-products of polymers soluble in the solvent.

A preferred composition of the copolymer has a propylene content of 70 to 70%.
99.95 mol%, the content of α-olefin having 2 to 12 carbon atoms is 0 to 15 mol%, and the content of branched 1°4-diene is 0.05 to 25 mol%, particularly preferably propylene content. is 75 to 99.5 mol%, carbon number 2 to 12
α-olefin content of 0 to 10 mol% and branched 1,
The 4-diene content is 0.5 to 20 mol%.

It is also possible to use unsaturated copolymers modified with maleic anhydride or the like.

(2) Branched 1,4-diene Specific examples of branched 1,4-dienes include 4-methyl-1,4-hexadiene, 5-methyl-1°4-hexadiene, 4-ethyl- 1,4-hexadiene, 4,5
-dimethyl-1,4-hexadiene, 4-methyl-1,
4-hebutadiene, 4-ethyl-1゜4-hebutadiene, 5-methyl-1,4-hebutadiene, 4-ethyl-1
, 4-octadiene, 5-methyl-1,4-octadiene, 4-n-7'ropyru, and particularly 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene are preferred.

These branched 1,4-dienes may be a mixture of two or more types, and in particular a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (mixing ratio: 95: 5 to about 5:95) is suitable.

(3) α-olefin having an IN prime number of 2 to 12 The α-olefin having 2 to 12 carbon atoms (excluding propylene) used in the present invention specifically includes ethylene, butene-1, hexene-1,4-methyl Pentene-1 and Octene-1
are preferred, and ethylene, butene-1 and hexene-1 are particularly important for practical purposes.

(4) Molecular weight The molecular weight of the copolymer of the present invention is such that the melt flow rate (MFR) measured in accordance with JIS K-6758 at 230°C and a load of 2.16 is 0.01 to 5001/10 minutes, preferably, The molecular weight corresponds to 0.05 to 2 oaf/1° min, particularly preferably 0.1 to 1 oaf/10 min. Outside this range, molding becomes difficult.

(5) Polymerization method The copolymerization method can generally use polymerization conditions using a Ziegler-Natsuta catalyst in which the transition metal component is a halogen-containing titanium compound or a composition thereof. That is, the polymerization temperature is 0 to 200°C, preferably 20 to 150°C.
°C, particularly preferably 30 to 100 °C, and the polymerization pressure is normal pressure to
150 #/ctI% preferably normal pressure ~ 90 #/d
, particularly preferably at normal pressure to 50 9/cl! is appropriate.

There is no particular restriction on the polymerization method, and the polymerization method may be a slurry method or a solution method using an inert solvent, or substantially no solvent is added, and one or more of propylene, α-olefin, and branched 1,4-diene serve as the solvent. without the use of slurry or solution methods or substantially liquid solvents,
Any method such as a gas phase method in which each monomer is kept in a substantially gaseous state can be applied to the present invention.

(6) Polymerization Catalyst The copolymer of the present invention can be produced using a Ziegler-Natsuta catalyst which basically consists of a halogen compound whose transition metal component is titanium or a composition thereof and an organometallic compound. Preferred is a stereoregular polymerization catalyst for α-olefin polymerization.

The titanium halogen compound or its composition is preferably a titanium chloride-containing solid catalyst component supported on a carrier such as titanium trichloride or magnesium chloride obtained by various manufacturing methods. As titanium trichloride, in particular, titanium tetrachloride is reduced with an organoaluminum compound, treated with a complexing agent, and further treated with a Lewis acid such as titanium tetrachloride, and a composition obtained by liquefying the titanium tetrachloride with a complexing agent is used. Examples include compositions obtained by precipitating titanium trichloride and preferably treating it with a Lewis acid such as titanium tetrachloride. Examples of the chloride-containing solid catalyst component of supported titanium include supported titanium components whose essential components are magnesium, chlorine, titanium, and electronic manuscripts. -82103,
54-94591, 55-59069, 58-1
9307, 58-32604, 58-32605,
58-117205, 58-183708, 59
-149905, 60-130607, patent application 1986-
45662, 60-53849, 60-54838
The solid catalyst components described in each issue can be exemplified.

The organometallic compound is preferably an organometallic compound of metals of groups I to II of the periodic table, and organoaluminum compounds are particularly preferred. Examples of organoaluminum compounds include compounds represented by the following formula.

Rn □ , n is a number expressed as 0 (n≦3).

In addition to the transition metal component and the organometallic component, it is also possible to add various compounds as a third component of the catalyst for various purposes, for example to improve stereoregularity. As this third component, an electron donor, iodine, etc. are preferably used. Examples of electron donors include carboxylic acid esters, sulfides, ethers, phosphyls, phosphine oxides, phosphoric acid amides, amines, organic antimony compounds, phosphoric esters, phosphites, and amine oxides. , silicate esters, etc.

The spinning unsaturated copolymer resin is spun alone or after being kneaded with the copolymer resin and a propylene resin.

As the propylene resin, a propylene homopolymer or a copolymer of propylene and a heptamer copolymerizable therewith can be used.

Examples of copolymerizable heptamers include α-olefins such as ethylene, butene, and hexene-1, and block polymers or random polymers of these and propylene are used.

Furthermore, it is also possible to use propylene resins modified with maleic anhydride or the like.

The content of the unsaturated copolymer resin is 1 to 100% by weight, preferably 1.5 to 80% by weight, more preferably 2.0 to 4% by weight.
It is 0% by weight. If it is less than 1% by weight, the effect of improving dyeability will be poor.

There are no particular restrictions on the spinning method, and propylene resin spinning technology can be used. Generally, it is spun by a melt spinning method.

The obtained filament may be a single yarn or may be a spun yarn. Further, other fibers may be blended as necessary.

Knitted fabrics In the present invention, knitted fabrics are used in a broad sense, and mean generally secondary processed products such as fabrics, knitted fabrics, and lace braids obtained using filamentous materials.

In addition to plain weave, twill weave, and satin weave, woven fabrics such as woolen fabrics such as velvet, tufted fabrics such as terry cloth, Welton carpet, touch rad carpet, etc., or knitted fabrics such as stockinette knitting and lace knitting can be used.

For woolen fabrics or tufted fabrics, the filamentous material of the present invention is used as pile yarn.

staining The knitted fabric is then dyed.

There are no particular restrictions on the dyeing method, and dip dyeing and printing, which are known as piece dyeing methods, can be used. method can be used.

As the dye, a known dye for propylene resin can be used, but since the knitted fabric of the present invention has excellent dyeability, a wide range of dyes for other synthetic fibers can be used.

(f) Experimental Examples The present invention will be explained in more detail with reference to Examples below.

Production of unsaturated copolymer resin 4-methyl-
An 8:2 mixture of 1,4-hexadiene and 5-methyl-1,4-hexadiene (hereinafter referred to as MI (abbreviated as D)), diethylaluminum chloride, and a titanium trichloride catalyst were charged, and then pressurized with propylene. Polymerization was carried out at a set temperature and pressure.The hydrogen concentration was kept constant during the polymerization.After the polymerization was completed, the catalyst residue was removed to obtain an unsaturated copolymer.The results are summarized in Table 1. 1 *1) JIS K-6758 *2) H-NMR 15 Examples-1 to 8 and Comparative Examples-1 to 2 Unsaturated copolymer resin obtained in Reference Example and polyglopyrene (Mitsubishi Yuka Noprene FY3VE) Using this, a 30d multifilament having the blending ratio shown in Table 2 was obtained.

These were stacked to form a thread-like material of 1000 d, and a carpet base fabric was woven using a loom.

This base fabric is made of acid dye xylene-fast-red P (
Sandoz Company trademark name)3%r)wf, H2SO46%,
When dyed in a dye bath containing 4% nonionic activator at a bath ratio of 50:1.90°C for 1 hour, it was dyed red. The fastness of this dyed product to sunlight and washing was JISS class. Furthermore, when dry cleaning properties were examined using perchlorethylene, excellent fastness was shown.

(Margin below)

Claims (1)

[Claims] At least propylene and a branch 1 represented by formula (I)
, 4 diene, and the content of the 1,4 diene is 0.
01-30 mol%, melt index 500g/1
A knitted fabric with excellent dyeing, characterized in that it is produced by knitting and weaving a filament obtained from a propylene polymer resin containing an unsaturated copolymer resin having a dyeing time of 0 minutes or less, and then dyeing it. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (Here, R^1 is an alkyl group with 8 or less carbon atoms, R^2
and R^3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms. However, R^2 and R^3 are not both hydrogen atoms. )