JPS6218448A - 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, that is, under relatively low temperature conditions, by blending an ethylene copolymer, an alkali metal salt of an org. carboxylic acid and a higher fatty acid amide 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. higher fatty acid amide compd. of formulas II and/or III (wherein R4, R5 are each H, a 1-4C alkyl; R6, R7, R8 are each a 10-24C alkyl; R9 is H, methyl; m, p, g are each 2 or 3) 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 Cζ that can be easily subjected to various molding processes and can be dyed extremely well with anionic dyes.

[Prior art] Poly-α-olefins such as polyethylene and polypropylene have excellent physical and mechanical properties and processability, but are also hydrophobic and chemically inert. However, it is extremely difficult to dye these molded products. Crystalline polypropylene fibers are especially light,
It has many features such as being strong and warm, and when it was first developed, it was expected to be used in a wide range of applications such as clothing as a ``dream fiber''. It is only used in limited applications such as 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 polypropylene with a substance that can serve as a dyeing seat for anionic dyes has the advantage that it does not impair the properties of polypropylene in terms of easy spinnability and yarn strength, and that it does not impair the properties of polypropylene in terms of easy spinnability and yarn strength. It is realistic and attracts attention in that it can be applied with a wide variety of dyes.

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

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, dyeing methods are also disclosed in JP-A-56-154588, JP-A-56-154584, JP-A-57-
No. 1331288, 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 the fibers obtained by spinning the various known dyeable polypropylene compositions as described above using the known improved dyeing methods as described above. However, it has been found that the dyeing time is 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 96°C using an acetic acid dye bath, the same type of 6-nylon yarn is dyed. Compared to the case of tufted carpet made from wool or spun yarn, the soaking time is 1.
It has been found that unless the length is increased to about 5 to 2 times, a satisfactory dye exhaustion rate cannot be obtained, resulting in insufficient fastness such as stiffness and 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 have conducted extensive research into improvements and have found that the combination with a specific higher fatty acid amide compound has a remarkable effect, leading to the present invention.

That is, the present invention provides one 100 tlt portion of a tetrapoly α-olefin, (B) ethylene and the general formula, (wherein R1 is hydrogen or a methyl group, R1 and R3 are hydrogen or an alkyl group having 1 to 4 carbon atoms) (C) an alkali metal salt of an organic carboxylic acid having 7 to 24 carbon atoms; 0.1 to 8 parts by weight and (DJ general formula, O or -〇〇-R,l (wherein, R4 and R are hydrogen or carbon number 1 to 4
The alkyl group, Ra # R? Katsu R6 has 1 carbon number
0 to 24 alkyl group, RQ is hydrogen or methyl group, m, p and q are integers of 2 or 3) A higher fatty acid amide compound represented by -0,1 to 5 layered lid part is melt-kneaded. The present invention relates to a dyeable poly-α-olefin archival composition with improved dyeability.

The feature of the dyeable poly-α-olefin combination acid according to the present invention is that it can be processed into fibers, chaves, films, sheets, etc. under substantially the same processing conditions as the poly-α-olefin that is the base of the composition. It can be easily processed into extrusion molded products, hollow molded products such as bottles, injection molded products such as containers and containers, and the molded products can be dyed in any color with general-purpose anionic dyes. It is.

Fibers or AM products obtained by melt spinning can be commonly applied to various dyeing methods and equipment, such as dip dyeing, continuous dyeing, and printing, which are widely used in the dyeing industry for nylon yarns, wool, etc. In addition, in any dyeing method, the dye penetrates deeply into the fibers, resulting in not only high dyeability but also excellent washing fastness, light fastness, and rubbing fastness.

Furthermore, the dye exhaustion rate is high even at the early stage of the dyeing process, that is, at low temperatures of about 60 to 70°C. Even when dyeing composites with other types of anion dyeable fibers that can be dyed at high speeds, such as blended yarns, twisted yarns, mixed knitted fabrics, etc., dyeing with little difference in shade is possible.

The contents of the present invention will be explained in detail below.

In the present invention, the component four polyα-olefins include:
In addition to crystalline homopolymers of α-olefins such as polyethylene, polypropylene, polybutene-1, poly-4 methylpentene-1, ethylene-propylene copolymers,
Various crystalline copolymers such as butenetopropylene copolymer, butenoateethylene copolymer, ethylene/vinyl acetate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl acrylate copolymer, etc. These include copolymers of ethylene and unsaturated ester comonomers such as polymers, saponified products of ethylene/vinyl acetate copolymers, etc., but the ones with particular industrial significance are melt index (JISK-6758) ) is 2 to 50
Polypropylene or propylene copolymer.

As the component used in the present invention (dialkylaminoalkyl acrylate comonomer for the Bl-ethylene copolymerization, various compounds described in Japanese Patent Publication No. 42-22528 are effective, but particularly preferred are Examples include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, etc. The aminoalkyl acrylate conomer unit in the ethylene copolymer is 1 to 50% by weight, preferably 10 to 85% by weight. %, and melt index (JISK-67
60) ranges from 1 to 1,000, preferably from 50 to 50
0. In addition to the aminoalkyl acrylate comonomer, vinyl acetate, vinyl propionate,
It may also be a ternary or higher copolymer containing one unit of an unsaturated ester comonomer such as methyl acrylate or methyl methacrylate in an amount of 20% by weight or less.

As a method for producing the ethylene copolymer (B), the high pressure method described in Japanese Patent Publication No. 58-6194 can be applied. That is, the ethylene pressure is 500 to 4,000 amperes,
Oxygen, organic peroxide,
It is produced by continuously contacting ethylene with an aminoalkyl acrylate compound having the above general formula in the presence of a free radical catalyst such as a diazo compound.

The appropriate amount of the ethylene copolymer (B) to be added is 1 to 20 parts by weight, preferably 5 to 10 parts per 7,100 parts by weight of the crystalline polyolefin. There is a problem that dyeability is insufficient, and if the amount added exceeds this amount, spinnability and yarn properties are impaired.

As C) the alkali metal salt of organic carboxylic acid having 7 to 24 carbon atoms, which is a constituent component of the composition of the present invention, JP-A No. 48
-111 such as those described in Publication No. 66646
Or two or more types are applied. For example, higher 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, 1,8-naphthylic acid, etc. aromatic acids and even nicotinic acids,
This includes sodium salts, potassium salts, lithium salts, aluminum salts, etc. of various organic acids.

Among these, sodium stearate, sodium benzoate, sodium pt-butylbenzoate, sodium nicotinate, potassium stearate, and potassium benzoate are preferred.

The amount of these organic carboxylic acid alkali metal salts added is 0.1 parts by weight per 100 parts by weight of poly-α-olefin.
8 parts by weight, preferably 0.2 to 2 parts by weight. If the amount added is less than the cough range, no effect will be achieved, and conversely, if the amount added is more than this range, not only will the corresponding deep dyeing effect not be enhanced, but the spinnability and physical properties of the yarn will be impaired.

In the dyeable poly-α-olefin composition of the present invention, p
) General formula or -Co-R.

(In the formula, R4 and R, are hydrogen or an alkyl group having 1 to 4 carbon atoms, R,, R,, Ra are alkyl groups having carbon aIO to 24, circles are hydrogen or methyl groups, m, p, and q are One or more higher fatty acid amide compounds represented by (representing an integer of 2 or 8) are included as an essential component in order to increase the dye exhaustion rate.

Each amide compound is prepared by using the corresponding primary amine compound or primary diamine compound as a raw material and adding one or more types of higher fatty acids having 10 to 24 carbon atoms in the presence or absence of a solvent and/or a catalyst. It is synthesized by heating at 120 to 250° C. for 2 hours or more under nitrogen atmosphere or vacuum conditions while stirring to cause a dehydration reaction.

Representative examples of the amide compound 0 include the following. Here, R represents a long-chain alkyl group having 10 to 24 carbon atoms, and particularly preferred are -q, 1, and -CI
I搗4, -C, TE■chi5, -C,. Toki 9, -C, 1H,
, etc.

C, H,, -NH-CH, -CH, -NH-Co-Ra
錇-NH-CHl-C錇-CH, -NH-CO-RR-
Co -NH-CH, -CH, -CH, -N-CH, -
CH, -CHl-NH-0-R CH.

R-CO-NH-CH, -CH2-C1(, -N -C
H2-CH,-CH,-Nf(-CO-R CHl R-CO-N)i-Ci(,-CE(,-CH,-N
-CH, -CH, -CH, -NH.

In the composition of the present invention, the higher fatty acid amide compound (
D) The total amount of 11 parts or 2 or more parts mixed is in the range of 0.1 to 5 parts, preferably 0.2 to 4 parts per 100 parts of poly-α-olefin. is within the range of Addition from this range/J)t! If the amount exceeds the above range, the effect of increasing the dye exhaustion rate will not be enhanced, and the washing fastness and yarn properties will be lowered. Not.

In the dyeable poly-α-olefin composition of the present invention, appropriate values of various additives such as heat stabilizers, antioxidants, ultraviolet deterioration inhibitors, antistatic agents, and flame retardants are added as necessary. It is also possible to add inorganic fillers or pigments.

Although there are no particular limitations on the method for producing the composition of the present invention,
The ingredients (~, (Bl, Gl and p)) and/or the various additives mentioned above are added to an extruder or Banbury mixer.
It is common to melt-knead and granulate polyalpha-olefin simultaneously or in stages at a temperature higher than the melting point of polyalpha-olefin, preferably from 200 to 280C, using a processing machine for resins.

The dyeable poly-α-olefin composition of the present invention usually has
By melt-spinning the base poly A-Ole 7 (under substantially the same processing conditions as in the case of polyamide 7), and further performing stretching, crimping, and spinning as necessary, it can be made into various DL or A fiber products. It is also possible to combine it with other types of chemical fibers or natural fibers.

The method of dyeing the fiber or textile product is the same as that for nylon thread or wool, and is described in Japanese Patent Application Laid-Open No. 58-1498, for example.
The method disclosed in Japanese Patent Application No. 89 is applicable.

In other words, inorganic acids or organic acids such as acetic acid, formic acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, oxalic acid, benzoic acid, salicylic acid, etc., and mixtures thereof, under moderately acidic conditions.
Anionic dyes such as acid dyes, metal-containing acid dyes, direct dyes, and acid mordant dyes are dissolved in the prepared dyeing bath, padding bath, or dyeing paste, and if necessary, various types of alkyl phosphates or their salts are dissolved. This is a method in which the fibers or textile products are brought into contact with each other in the coexistence of dyeing aids, leveling agents, slow dyeing agents, sizing agents, etc. and heated to around 100°C.Practically speaking, various dyeing methods and continuous dyeing methods are used. method, printing method, etc. can be applied.

Since it can be melt-processed into products of various shapes, such as tubes, and can be dyed in any color tone, it is of great industrial significance in terms of opening up a wide range of applications for 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 (overlapping % per fiber) and dyeing aid electro stripper e) K (manufactured by Kao Atlas Co., Ltd., potassium salt of alkyl phosphate) A bath ratio consisting of 8% owf Predetermined amounts of various dyes are dissolved in a 1:60 dye bath and heated to 50°C. Various fiber samples B gr 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.
After reaching ℃, staining is continued for 80 minutes.

The dyed fiber sample was taken out, washed with water, and sieved at 60°C for 5 minutes in a bath containing Monoken (manufactured by Dai-Kogyo Seiyaku Co., Ltd., sodium salt of alkyl sulfate ester) 2/e at a bath ratio of 1:60. This was followed by further washing with water and drying.

(2) D R70 (dye exhaustion rate at 70°C) During the heating process of the above dyeing method, when the bath temperature reached 70°C, approximately 2 ml of the bath liquid was sampled, and the remaining dye concentration was determined by colorimetry. Measure and calculate. In other words, if the absorbance of the dye solution before dyeing at the dye's specific absorption wavelength is a, and the absorbance of the bath solution collected at 70°C is b, then 100x(a-b)/a is '%.
jetl,ru.

(31DRloo (final exhaustion rate at 100℃) 100℃
Letting C be the absorbance of the bath solution after dyeing for 80 minutes at the absorption wavelength specific to the dye, 100 K (a-C)/a-f-rare.

(4) FR (Final Dyeing Ratio) If the absorbance of the residual liquid after soaping at the absorption wavelength specific to the dye is d, it is given by PR-DRloo-100d/a.

(5) Light fastness: Compliant with JISL-0842 The light source is carbon arc. The color tone after irradiation at 68° C. for 80 hours was compared with blue scale and judged. Grade 1 (worst) to grade 8 (best).

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

5 The load was 200fr, and damp cotton (JISL080B
) after rubbing 100 times at a frequency of 80 times/minute. Grade 1 (worst) to grade 5 (best).

Examples 1 to 11 Various dyeable polypropylene compositions (I) c-1 to 1 shown in Table 1 were prepared using an 8 Q m d extruder (L/D = 20).
DC-9) was prepared in 1O- each. That is, in addition to predetermined amounts of four types of components consisting of polypropylene, ethylene copolymer, organic carboxylate, and amide compound, Kuruga Knox [F] 1010 (manufactured by Ciba Iggy Co., Ltd. > 0.1 Parts by weight and 0.5 parts by weight of Sumi Nobu ■300 (Sumiman Kagaku!!!) as an ultraviolet absorber were mixed in a Henschel mixer, and then melt-kneaded by extrusion to obtain composition pellets. Next, the pellets were fed to a spinning machine equipped with a 12-hole nozzle with a hole diameter of 0.8u at the tip of a 25sa extruder (L/D = 15), and the resin temperature was 2.40℃, the extrusion rate was 1ml noodles/h, and the winding was performed. Taking speed 420
Melt spinning was carried out under the conditions of 11 m/min, and then 11
The sample was stretched 3 times by running a hot plate at 0° C. to obtain a multifilament sample of 11 denier/filament. Although the operation was continued for 8 hours, there was no yarn breakage in any of the compositions, and homogeneous multifilaments with smooth and glossy surfaces were obtained.

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

Comparative Examples 1 to 11 Various dyeable polypropylene compositions (FR-1-FR- 5) was adjusted.

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
It was inferior to the case of a composition containing a compound, and in particular, DR and +stiffness were at extremely low levels.

〔Effect of the invention〕

As described 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. Even at the initial stage of the process, it is possible to provide a dyeable polypropylene composition having a dye exhaustion rate comparable to that of nylon yarn or wool.

P-1, Noblen [phase] FL800 (manufactured by Sumitomo Chemical Co., Ltd., polypropylene, homopolymer grade MFI standard 10° JISK-6760 compliant), pellet-like R-2 Noblen (lOWF727R (manufactured by Sumitomo Chemical Co., Ltd., polypropylene, random copolymer grade, ethylene) Kyohai 114
Contributing children %, MFI=80. JIS-6760 Table #&) E-1; Copolymer of ethylene and dimethylaminoethyl methacrylate in a weight ratio of 74/26 (MFI = 95°J
ISK-676 (based on l), pelleted E-2, copolymer of ethylene and diethylaminoethyl acrylate in a 70/80 weight ratio (MFI wet 210° JISK-6760
S-2i containing S-1 in pellet form + sodium 4 of higher fatty acid mixture (6 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 parts by weight of water Sodium benzoate, finely ground crystalline powder CH.

N-t, C1? H,, -CO-NH-CH,CH,C
H, -N-CH, CH, CH.

-XHi-CO-C, ), iO flaky wax N-2; ζ, 1-IS, -Co-:()i -C
k-1, CH, CH, -N-C 錇CH1CH.

-1Jti-CU-NitAs flaky wax CI.

Claims (4)

[Claims] (1) For (A) poly-α-olefin, 100 parts by weight, (B) ethylene and the general formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is hydrogen or a methyl group, R_2 and R
_3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4. ) 1 to 20 parts by weight of a copolymer with a dialkylaminoalkyl acrylate comonomer represented by (C) 0.1 to 3 parts by weight of an alkali metal salt of an organic carboxylic acid having 7 to 24 carbon atoms; ) General formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Z; H or -CO-R_8 (In the formula, R_4 and R_5 are hydrogen or carbon number 1 or 4 alkyl group, R_6, R_7, R_8 have 1 carbon number
0 to 24 alkyl group, R_9 is hydrogen or methyl group, m, p and q represent integers of 2 or 3), 0.1 to 5 parts by weight. Dyeable poly-α-olefin composition. (2) A patent in which component (C) the alkali metal salt of an organic carboxylic acid is a metal salt of one or more acids selected from sodium salts or potassium salts of higher fatty acids having 10 to 24 carbon atoms or benzoic acid. The dyeable poly-α-olefin composition according to claim 1. (3) The dyeable poly-α-olefin composition according to claim 1 or 2, wherein component (A) poly-α-olefin is polypropylene. (4) Component (D) higher fatty acid amide compound is the following N-
The dyeable poly-α-olefin composition according to claim 1 or 2, which is one or more compounds selected from 1 to N-6. N-1; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ N-2; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ N-3; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ N-4; ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ N-5; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ N-6; C_2H_5-NH-CH_2CH_2-NH
-CO-C_2_1H_4_3