JPS6218449A - Dyeable poly-alpha-olefin composition - Google Patents

Abstract

PURPOSE:To improve the dye exhaustion rate to a level comparable to that of nylon or wool even at the initial stage of a dyeing step, by blending an ethylene copolymer, an alkali metal salt of an org. carboxylic acid and a dialkylamine compd. and/or a dialkylamino ester compd. with a poly-alpha-olefin. CONSTITUTION:1-20pts.wt. copolymer of ethylene and a dialkylaminoalkyl acrylate comonomer of formula I (wherein R1 is H, methyl; R2, R3 are each H, a 1-4C alkyl; n is an integer of 1-4), 0.1-3pts.wt. alkali metal salt of a 7-24C org. carboxylic acid and 0.1-5pts.wt. dialkylamine of formula II and/or dialkylamino ester compd of formula III (wherein R4, R5, R6, R8 are each a 10-24C alkyl; m is an integer of 1-5) are blended with 100pts.wt. poly-alpha-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to dyeable polyolefin compositions. More specifically, the present invention relates to a dyeable poly-α-olefin composition that can be easily subjected to various molding processes and can be dyed extremely well with anionic dyes.

[Conventional technology]

Although poly-α-olefins such as polyethylene and polypropylene have excellent physical and mechanical properties and processability, they are hydrophobic and chemically inert, making them difficult to mold. It is extremely difficult to dye. In particular, crystalline polypropylene fibers have many features such as being light, strong, and warm, and when they were first developed, they were considered a "dream fiber" and were expected to be used in a wide range of applications such as clothing. Due to its drawbacks, it is used only in limited fields of application, such as uncolored futon cotton and carpet pile yarn colored with inorganic pigments.

For this reason, there has been a strong desire to improve the dyeability of polypropylene fibers, and many methods have been proposed to date.

For example, the method of melt spinning by adding and mixing a substance that can serve as a dyeing seat for anionic dyes to polypropylene has the advantage that it does not impair the properties of polypropylene in terms of easy spinnability and yarn strength, and that it is similar to nylon yarn and wool. It is realistic and attracts attention because it can be applied with a wide variety of common dyes.

Among them, the copolymer of ethylene and aminoacrylate compound described in Japanese Patent Publication No. 42-22528 has good thermal stability and is dispersed extremely finely and uniformly in propylene by melt mixing. , provides a dyeable polypropylene composition with excellent spinnability.

Also, JP-A-48-66646 and JP-A-59-4
Japanese Patent No. 1845 discloses the effect of improving dyeability by further adding various metal salts of organic carboxylic acids to the above composition.

On the other hand, regarding the dyeing method
Publication No. 154584/1984, Japanese Patent Application Laid-open No. 1987-154584
JP-A-188288, JP-A-58-149889, and JP-A-59-1786 disclose the effects of using various dyeing aids and dyeing oils.

[Problem that the invention seeks to solve]

However, according to numerous practical tests conducted by the inventors,
When fibers obtained by spinning various known dyeable polypropylene compositions as described above are actually dyed using dyeing equipment widely used in the dyeing industry, it is also possible to dye them using the known improved dyeing methods as described above. It has been found that the dyeing time becomes uneconomically long due to the slow exhaustion rate of the dye.

For example, when dyeing a tufted carpet made from fibers obtained from the ternary dyeable polypropylene composition as pile yarn at 95°C using an acetic acid dye bath, the same type of 6-nylon yarn Compared to the case of tufted carpets made from wool or spun yarn, the soaking time is 1.
．． A satisfactory dye exhaustion rate cannot be obtained unless the length of time is 5 to 2 times, and if the length of time is shorter than this, the dyeing property is insufficient and only the surface of the yarn is dyed, resulting in poor washing fastness, light fastness, etc. It was found that the properties were insufficient in terms of various fastnesses such as abrasion resistance.

The object of the present invention is to solve these problems and to produce dyeable polyester fibers that have a dye exhaustion rate on the same level as nylon yarn or wool even in the early stages of the dyeing process, that is, in the relatively low temperature region.
An object of the present invention is to provide an α-olefin composition.

[Means for solving problems]

In view of this situation, the inventors of the present invention conducted intensive research into improvements and found that the combination effect with a specific higher fatty acid amide compound is remarkable, leading to the present invention.

That is, the present invention provides: (6) poly-α-olefin, per 1 part of 100flii @ ethylene and the general formula (wherein R1 is hydrogen or a methyl group, Rt and α゛IR
8 is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is 1
A copolymer with a dialkylaminoalkyl acrylate comonomer represented by (integer from 1 to 4), 1
~20 parts by weight, and 0 alkali metal salt of organic carboxylic acid having 7 to 24 carbon atoms, 0.1 to 8 parts by weight, plus 0 general formula, Ra-NH-
Rs OJ: Hi/t Tast (in the formula, Ra,
R5, Rs, Rt and R8 have 10 to 2 carbon atoms
4 alkyl group, R. is hydrogen or methyl group, m is an integer of 1 to 6) 0.1 to 5 parts by weight of a dialkylamine compound and/or dialkylamino ester compound represented by 200 to 200 parts by weight The present invention relates to a dyeable poly-α-olefin composition with improved dyeability obtained by melt-kneading in a temperature range of 280°C.

A feature of the dyeable Bori-α-olefin composition according to the present invention is that it can be used to produce extruded products such as fibers, tubes, films, and sheets under substantially the same processing conditions as the poly-α-olefin that is the base of the composition. It is easy to process into hollow products such as bottles and bottles, injection molded products such as containers and hangers, and the molded products can be dyed well with general-purpose anionic dyes. The application is important from an industrial point of view. That is, fibers or textile products obtained by melt-spinning the composition of the present invention can be dyed using various dyeing methods such as dip dyeing, continuous dyeing, and printing, which are widely used in the dyeing industry for nylon yarns, wool, etc. As the equipment can be commonly applied, and as a result of the dye penetrating deep into the fibers in any dyeing method, not only high dyeing properties can be obtained, but also fastness to washing, light fastness, rubbing fastness, etc. Excellent in points as well. Furthermore, at the initial stage of the dyeing process, i.e. 50~
Since the dye exhaustion rate is high even under low temperature conditions of about 70°C, the fibers obtained from the composition of the present invention can be combined with other types of anion dyeable fibers such as nylon yarn and/or wool, which have a high dye exhaustion rate. Even when dyeing a composite, such as a blended yarn, interlaced yarn, or mixed knitted fabric, it is possible to dye the product with little difference in shade.

Hereinafter, the content of the present invention will be explained in detail.

Component (A) poly-α-olefin in the present invention includes polyethylene, polypropylene, polybutene-1,
In addition to crystalline homopolymers of a-olefins such as poly-4-methylpentene-1, various crystalline copolymers such as ethylene/propylene copolymers, butenetopropylene copolymers, butenetoethylene copolymers, etc. Copolymers of ethylene and unsaturated ester comonomers, such as ethylene/vinyl acetate copolymers, ethylene/methyl methacrylate copolymers, ethylene/ethyl acrylate copolymers, and ethylene/acetic acid copolymers. This includes saponified vinyl copolymers, but the ones that are of particular industrial significance are:
It is a crystalline polypropylene polymer or copolymer.

Various compounds described in Japanese Patent Publication No. 42-22528 are effective as the dialkylaminoalkyl acrylate comonomer for the zero-component tyrene copolymer used in the present invention, but particularly preferred are as dimethylaminoethyl methacrylate,
Examples include diethylaminoethyl methacrylate and dimethylaminoethyl acrylate. The aminoalkyl acrylate conomer unit in the ethylene copolymer is 1 to 50% by weight, preferably 10 to 85% by weight, and has a melt index (JIS K6
760) ranges from 1 to 1.000, preferably from 50 to 5
00.

In addition to the aminoalkyl acrylate comonomer, if one unit of an unsaturated ester comonomer such as vinyl acetate, vinyl propionate, methyl acrylate, or methyl methacrylate is contained within a range of 20% by weight or less, the Copolymers of the above may also be used.

The method for producing the ethylene copolymer is described in Japanese Patent Publication No. 58
The high pressure method described in JP-A-6194 can be applied. That is, ethylene pressure 500 to 4,000Kt/-
1 temperature 1oo~3o.

It is produced by continuously bringing ethylene into contact with an aminoalkylaqueous compound having the above general formula in the presence of a free radical catalyst such as oxygen, an organic peroxide, or a diazo compound at ℃. Ru.

The appropriate amount of the ethylene copolymer 0 to be added is 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based on too many parts of the crystalline polyolefin. If the amount added is below this range, the dyeability will be insufficient, and if the amount added above this range, the spinnability and yarn properties will be affected. 111 or two or more of the following are applicable. For example, highly concentrated fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, benzoic acid, pt-butylbenzoic acid, phenylacetic acid, and 1,8-naphthylic acid. Aromatic acids such as nicotinic acids, various sodium salts,
This includes potassium salts, lithium salts, aluminum salts, etc. Among them, sodium stearate, sodium benzoate, sodium pt-butylbenzoate, and sodium nicotinate are preferred.The amount of these organic carboxylic acid alkali metal salts to be added is 10 parts by weight of poly-α-olefin. 0.1 against
-8 parts by weight, preferably 0.2-2 parts by weight. If the amount added is less than this range, no effect will be obtained, and if it is added more than this range, the corresponding deep dyeing effect will not be improved, and the spinnability and physical properties of the yarn will be impaired.

The dyeable poly-α-olefin composition of the present invention contains 0
A dialkylamine represented by the general formula, (wherein R4 and 6 represent an alkyl group having 10 to 24 carbon atoms), or/and a dialkylamine represented by the general formula (wherein, Re, R?, Rs are carbon numbers 10 to 24 alkyl group, R9 is hydrogen or methyl group, m
is an integer from 1 to 6) is contained as an essential component for increasing the exhaust rate.

Representative examples of dialkylamines include distearylamine, dilaurylamine, dialkylamine, civalmitylamine, and the like.

Further, dialkylamino ester compounds are obtained by subjecting the dialkylamines mentioned above to an addition reaction with ethylene oxide or propylene oxide, and then esterifying the mixture with various higher fatty acids. Typical examples thereof include distearyl aminoethyl stearate, Examples include distearyl aminotrioxyethylene stearate and dilaurylaminotrioxypropylene stearate.

The total amount of the dialkylamine or/and dialkylamino ester compound added is in the range of 0.1 to 6 parts by weight, preferably in the range of 0.2 to 4 parts by weight, based on 100 parts by weight of the poly-α-olefin. be. If the amount added is less than this range, no effect will be achieved, and if it is more than this range, the effect of increasing the dye exhaustion rate will not be enhanced, and the washing fastness may decrease or the yarn properties may deteriorate. is not appropriate because it reduces

In the dyeable poly-α-olefin composition of the present invention, various appropriate additives such as heat stabilizers, antioxidants, ultraviolet deterioration inhibitors, antistatic agents, and flame retardants may be added as necessary. Furthermore, it is also possible to add a small amount of inorganic filler or pigment.

Although there are no particular limitations on the method for producing the composition of the present invention,
The component direction, @, (Q, and 0 and/or the various additives mentioned above) are processed in a resin processing machine such as an extruder or a Banbury mixer to a temperature higher than the melting point of the poly-α-olefin, preferably 2.
Generally, granulation is carried out by melting and kneading at 00 to 280° C. simultaneously or in stages.

The dyeable poly-α-olefin composition of the present invention usually has
It can be made into various fibers or textile products by melt spinning under substantially the same processing conditions as for the base stream-α-olefin, and further stretching, crimping, or spinning as necessary. In addition, the same applies to other types of chemical fibers, natural fibers, braided yarns, and wool; for example, JP-A-5.8-
The method disclosed in Japanese Patent No. 149889 is applied. That is, U-free substances such as acetic acid, formic acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, oxalic acid, benzoic acid, salicylic acid, etc.
In a dyeing bath, padding bath or dyeing paste adjusted to moderately acidic conditions with an acid or an organic acid or a mixed acid thereof,
Dissolves anionic dyes such as acid dyes, metal alloy dyes, direct dyes, and acidic mordant dyes, and, if necessary, various dyeing aids such as alkyl phosphates or their salts, leveling agents, loosening dyes, sizing agents, etc. This is a method in which the fibers or textile products are brought into contact with each other and heated to around 100°C.Practically speaking, various dip dyeing methods, continuous dyeing methods, printing methods, etc. can be applied.

The dyeable poly α-olefin composition according to the present invention can be melt-processed into mallet-shaped products such as films, sheets, and tubes in addition to fibers, and can be dyed in any color. This is of great industrial significance in terms of expanding the fields of application of poly-α-olefins.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way.

The dyeing of the fiber samples and the evaluation of dyeing properties and color fastness were carried out by the following methods.

(1) Dyeing method Acetic acid or formic acid 2% OWF (wt% per fiber) and dyeing aid Electrostritz 7, -■K (
A predetermined amount of various dyes was dissolved in a dye bath consisting of 8% OWF (potassium salt of alkyl phosphate, manufactured by Yaea Uyu Co., Ltd.) at a bath ratio of 1:60, and heated to 50°C. Various fiber samples Bgr were immersed in the dyeing bath at 50°C, and the temperature was raised at a rate of 1°C/min while stirring up and down.
Continue staining for aO min after 0°C (U1).

Soaping was carried out at 60° C. for 5 minutes in a soaping bath containing sodium salt of alkyl sulfate 21/L at a bath ratio of 1:60, followed by washing with water and drying.

(2) DR7G (70tt'(7) dye exhaustion rate)
During the heating process of the above dyeing method, when the bath temperature reaches 70'C, about 200 ml of solution is sampled, and the remaining dye concentration is measured and calculated by colorimetric method.

That is, if the absorbance of the dye solution before dyeing at the absorption wavelength specific to the dye is a, and the absorbance of the bath solution collected at 70°C is b, then it is given by 100X(ab)/a.

``' DRloo (at 100 tl) f & final exhaustion rate) If the absorbance of the bath solution after dyeing at 100°C for 80 minutes at the dye's specific absorption wavelength is C, then 100 X (a-c
)/a.

(4) PR (final dyeing rate) -100d/a.

(ω Light resistance...based on JISL-Q842.

The light source was a carbon arc, and the color tone after irradiation at 68° C. for 80 hours was compared with blue scale. Grade 1 (worst) to grade 8 (best).

(6) Fastness to friction: Compliant with JISL-0849.

The load is 200gr, wet cotton (JISL0808)
Judgment was made after rubbing 100 times at a frequency of 80 times/minute.

Grade 1 (1tM) to Grade 5 (best).

Examples 1 to 11 80 m d (D extruder (L/D = 20) scr dyeable polypropylene composition (DC-
1~DC-g) t,, each 10KLI preparation site.

That is, in addition to predetermined amounts of four constituents consisting of 4'lipropylene, ethylene copolymer, organic carboxylic acid salt, and N-containing compound, Irganox 1010 (manufactured by Ciba Geigy) was used as a stabilizer.
0.1 part by weight, and 1-□b■ as an ultraviolet absorber
8゜0 (manufactured by Sumitomo Chemical). , 5 parts by weight were mixed in a Henshi Flum mixer, and then melted and kneaded in an extruder to obtain composition pellets. The material was supplied to a spinning machine equipped with a 12-hole nozzle with a hole diameter of 0.8 cm, and melt-spun was carried out under the conditions of a resin temperature of 240°C, an extrusion rate of 1-/h, and a winding speed of 420 m/min. A hot plate was run and the sample was stretched 8 times to obtain a multifilament sample of 11 denier/filament. Although it was operated continuously for 8 hours, there was no thread breakage at all in any of the compositions.
It was a homogeneous multifilament with a smooth and glossy surface.

The various multifilament sample yarns thus prepared were dyed with acid dyes or metal-containing acid dyes shown in Table 2 in an acetic acid or formic acid bath, and then soaped. Both fastness and tearing were good, and DR7G was also at a high level.

Comparative Examples 1 to 10 Various dyeable polypropylene compositions (FR-1 to FR- 6) was prepared. The composition was spun and drawn using the same spinning machine and under the same conditions as in Example 1 to prepare a 16 denier/filament multifilament sample yarn, which was further dyed using the same method and under the same conditions as in Example 1 to obtain the results shown in Table 2. The dyeability and fastness results were obtained as shown in .

Regarding spinnability, there were no problems with any of the compositions, and the yarn quality was uniform and good, but in terms of dyeability and fastness, the N-containing
Compared to the case of compositions containing compounds, the DR? Regarding G, the level was extremely low.

〔Effect of the invention〕

As explained above, according to the present invention, it is possible to obtain a poly-α-olefin composition having extremely superior dyeing properties compared to conventional dyeable polypropylene compositions, etc. Lipropylene compositions and the like can be provided.

Table 1 P-1; /--jlz, ■FL800 (1.

Pyrene, homopolymer grade MFI=10, JIS
K-6760 compliant), pellet-like P-2; Noblen 0
WF727R (manufactured by Sumitomo Chemical, polypropylene, random copolymer grade, ethylene copolymerization 114%, M
FI=80, according to JIS-6760), pellet E-1; copolymer of ethylene and dimethylaminoethyl methacrylate with a polymorphism ratio of 74/26 (MFIss, J
ISK-8760 compliant), pellet E-2; copolymer of ethylene and diethylaminoethyl acrylate in a 70/80 weight ratio (MFI=210, JISK-6760
), pellet form S-1; sodium salt of high PJt fatty acid mixture (5 parts by weight of sodium myristate, 80 parts by weight of sodium palmitate, 65 parts by weight of sodium stearate) in the form of flakes, containing 8" Mt part of water. S-2; Am, !L fragrant sl/lium, finely ground crystal S-8
; Sodium nicotinate, finely ground crystals s-4. ;pt
- Sodium butyl benzoate, finely ground crystals N-1; distearyl aminoethyl stearate, flakes N-2; distearyl aminoethyl behenate, flakes N-8; distearylamine, flakes N-
-4; Distearylaminotrioxyethylene stearate, flaky N-5; Dibehenylamine, flaky N-6; Dilaurylaminotrioxyethylene behenate, flaky

Claims (5)

[Claims] (1) For (A) poly-α-olefin, 100 parts by weight, (B) ethylene and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is hydrogen or a methyl group, R_2 and R
_3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 4) A copolymer with a dialkylaminoalkyl acrylate comonomer,
1 to 20 parts by weight, (C) 0.1 to 3 parts by weight of an alkali metal salt of an organic carboxylic acid having 7 to 24 carbon atoms, and (D) General formula, R_4-NH-R_5 and/or ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_4, R_5, R_6, R_7 and R_8
is an alkyl group having 10 to 24 carbon atoms, m is 1 to 5
dialkylamine compounds and/or dialkylamino ester compounds represented by (representing an integer of ),
A dyeable poly-α-olefin composition comprising 0.1 to 5 parts by weight. (2) Component (C) The alkali metal salt of organic carboxylic acid is an alkali of one or more acids selected from higher fatty acids having 10 to 24 carbon atoms, benzoic acid, pt-butylbenzoic acid, and nicotinic acid. The dyeable poly-α-olefin composition according to claim 1, which is a metal salt. (3) The dyeable poly-α-olefin composition according to claim 1 or 2, wherein component (A) poly-α-olefin is polypropylene. (4) The dyeable poly-α- according to claim 1 or 2, wherein the dialkylamine compound (D) is distearylamine and/or dibehenylamine.
Olefin composition. (5) Component (D) The dialkylamino ester compound is selected from distearyl aminoethyl stearate, distearyl aminoethyl behenate, distearyl amino trioxyethylene stearate, and dilauryl amino trioxyethylene behenate 1 seeds or 2
Claim 1 or 2 which is a compound of more than one species
The dyeable poly-α-olefin composition described in 1.