JPS5842311B2 - Senshiyokusei no Kaizensareta Jinkou Hikaku - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to artificial leather with improved dyeability.

Conventionally, various artificial leathers have been proposed that are made of fiber entangled bodies such as nonwoven fabrics using polyethylene terephthalate fibers and binder polymers such as polyurethane and acrylic resins.

In particular, it is well known that artificial leather using polyurethane having high molecular elasticity as a binder component has excellent flexibility and formability.

However, when dyeing the artificial leather, since the constituent fibers of the artificial leather are polyethylene terephthalate fibers, the actual situation is that the artificial leather is dyed with a disperse dye commonly used for such fibers.

Disperse dyes are usually inferior in sharpness compared to ionic dyes.

Furthermore, the polyurethane constituting the artificial leather is extremely dyeable with disperse dyes compared to polyester fibers.

Therefore, when dyeing the artificial leather with a disperse dye, the disperse dye is naturally preferentially dyed in the phase between these two components that has good dyeability.

That is, as a result, most of the dye is dyed on the polyurethane side, causing a decrease in dye utilization rate with respect to polyester.

Furthermore, it is well known that disperse dyes have a low affinity for polyurethane, and therefore, the laundry room waxiness and light fastness waxiness of dyed products are a practical problem in the artificial leather.

These problems become more noticeable in suede-like artificial leathers made of entangled polyester fibers of ultra-fine fineness that have recently been commercially available.

In other words, in the case of artificial leather made of such ultra-fine fiber entanglement and a polyurethane polymer binder, the fibers are thin, so when dyeing a deep color, the dye concentration is higher than when dyeing ordinary fabric. dye.

Therefore, the amount of distributed dyeing of the disperse dye on the polyurethane becomes even larger, and as a result, the dye fastness becomes worse.

Therefore, there is a demand for artificial leather having dyeing properties in which the ester fibers are well dyed, and the amount of polyurethane dyed is rather low.

The inventors of the present invention have conducted extensive research to improve these drawbacks, and have found that by using fibers modified with a specific modifier as the polyester fibers used, the above-mentioned properties can be achieved while retaining the properties suitable for artificial leather. The inventors have discovered that dyeability can be significantly improved and have arrived at the present invention.

That is, the present invention provides a fiber entangled body comprising a copolymerized polyester fiber containing one or more compounds represented by the following formula (I) in an amount of 0.5 to 20 moles relative to the acid component which is a structural unit of the polyester. and a binder made of a polyurethane polymer, which is an artificial leather with improved dyeability.

[However, R: alkyl group, K, R: the same or different alkylene group having 3 to 8 carbon atoms, preferably 3 to 4 carbon atoms, -
'2 y m : A value indicating the degree of polymerization of the polyoxyethylene group, which is a positive number that satisfies the relationship 10≦i+m≦30.

] The polyester constituting the artificial leather of the present invention refers to an aromatic polyester, which is composed of one or more acid components whose main components are aromatic dicarboxylic acids or lower alkyl esters thereof, and one or more glycols. It is a polyester that is polymerized from more than one species.

Aromatic dicarboxylic acids are terephthalic acid, naphthalene-2
, 6-dicarboxylic acid, diphenyldicarboxylic acid, diphenyl etherdicarboxylic acid, ethylene-1,2-bis(
p-carboxyphenoxide), p,p'-disulfonylbenzoic acid, and so on.

What is glycol? Polymethylene glycol having 2 to 10 carbon atoms, cyclohexane dimetatool, p-xylene diol, benzene-1,4-bis(β-oxyethoxide)
etc.

In addition to the basic polyester components, isophthalic acid, phthalic acid, oxalic acid, adipic acid, cepatic acid, 6,
6-disulfonylcaproic acid, diethylene glycol,
It is also possible to copolymerize by adding a small amount of triethylene glycol, polyethylene glycol, neopentyl glycol, bisphenol A1 pentaerythritol, etc.

The polyester fiber used in the present invention includes the above-mentioned polyester component and a compound represented by the above-mentioned general formula (1) (sometimes simply referred to as a modifier) in an amount of 0.5 to 2% relative to the acid component.
It is necessary to carry out 0 molar copolymerization.

Copolymerization here refers not only to binding to the main chain of the polyester polymer, but also to copolymerization in which a portion of the modifier remains unbound and exists together with the polyester polymer. It includes.

Examples of the modifier represented by the above general formula include the following.

As the modifier used in the present invention, the sum of the polymerization degrees of polyoxyethylene constituting the two substituents is 10
~30 is preferred.

If the sum of the degrees of polymerization of polyoxyethylene is 9 or less, the polymer obtained in the production of polyester will be colored and the dyeability will be insufficient.

Furthermore, when the sum of the degrees of polymerization of polyoxyethylene is 31 or more, it is necessary to add a large amount of the modifier in order to impart dyeability to the polyester, which causes the resulting polymer to be colored.

In order to impart dyeability with acid dyes, the amount of the modifier added is 0.5 to 20% of the acid component of the basic polyester.
Although a molar width is required, the molar width is preferably 10 molar or less in terms of the colorability of the polymer obtained by modification.

The polymerization reaction of the polyester can be carried out using the reactants in a molten state or in a solid state according to known methods.

The above-mentioned modified polyester used in the present invention is dyeable with ionic dyes such as acid dyes and acid mordant dyes.

That is, when artificial leather made using the polyester fiber obtained by the above copolymerization is dyed with an ionic dye such as an acid dye or an acid mordant dye, the polyester fiber is dyed extremely well.

On the other hand, polyurethane, which will be described later, is hardly dyed by ionic dyes.

Therefore, in the artificial leather of the present invention, the dyeing fastness of polyurethane does not deteriorate, and the fibers can be dyed well, making it possible to obtain a desirable product.

In addition, since ionic dyes have good affinity with the dyeable material, they have the advantage that the dye utilization rate of ionic dyes is high compared to dyeing methods using disperse dyes.

The fibers forming the constituent components of the artificial leather are produced by spinning using a known melt spinning method.

That is, the modified polyester of the present invention is spun alone.

Polyester and other polymers are combined and spun into a multicomponent fiber with polyester as an island component (or core component or fine fiber component) and other polymers as a sea component (or sheath component).

For example, two types of polymers are spun using a special multi-core/sheath type mixed spinning method as typified by Japanese Patent Publication No. 39-29636 and Japanese Patent Publication No. 44-18369. A spinning method to obtain a sea-island structure fiber by performing an operation, a spinning method to obtain a sea-island structure fiber by passing two polymers through a static mixer, and a so-called chip blend mixed spinning method in which the two polymers are mixed in the form of chips and spun. etc. can be adopted.

Examples of the method for producing the fiber entangled body include forming a fibrous nonwoven web by a known dry method or wet method, and manufacturing the fibrous nonwoven web by a punching method using a needle punch, an air jet, or a water jet.

Preferably, the entangled body is formed by needle punching.

Furthermore, the fiber may be a fabric obtained by knitting, weaving, etc., or a raised fabric thereof.

The polyurethane used in the artificial leather of the present invention includes one or more diisocyanate components and one or more diisocyanate components.
It is a polymer whose main chain is composed of urethane bonds produced by reacting one or more polymer diol components with a chain extender.

Examples of the diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, biphenyl isocyanate, hexane diisocyanate, and cyclohexane diisocyanate.

Polyester diol components include polyesters formed from dicarboxylic acids and dihydric alcohols, such as polyester diols from adipic acid and diethylene glycol, polyester diols from adipic acid and butylene glycol, and polyester diols from adipic acid, ethylene glycol, and propylene glycol. Examples include polyester diols such as, polyalkylene ether glycols such as polyethylene ether glycol, polypropylene ether glycol, and polybutylene ether glycol, and polycaprolactone glycol.

In addition, as a chain extender, a compound having two active hydrogen atoms, such as ethylenediamine, hexamethylenediamine,
Examples include diamines such as dicyclohexylmethanediamine, and glycols such as ethylene glycol, propylene glycol, and butylene glycol.

Artificial leather can be manufactured by using the above-mentioned polyester fibers and polyurethane and applying a known method. For example, the above-mentioned polyester fiber nonwoven fabric is immersed in a polyurethane solution or polyurethane emulsion, and then the polyurethane is wet-coagulated. Alternatively, dry coagulation is performed to coagulate the polyurethane as a microporous elastic body, and the polyurethane is used as a binder for the fiber entangled body.

A more preferred embodiment of the present invention is suede-like artificial leather using ultrafine fibers, which is produced, for example, by the following method.

The fiber entanglement obtained by the multicomponent fiber spinning method described above is immersed in a polyurethane solution or polyurethane emulsion, the polyurethane is wet-coagulated or dry-coagulated, and then treated in a sea-component solvent or decomposition agent to form the fibers. The sea component polymer is removed to obtain a fiber entangled body consisting of ultrafine polyester fibers with an average fineness of 0.1 denier or less (preferably an average fineness of 0.05 denier or less).

After the obtained artificial leather is dried, the surface is puffed to obtain an artificial leather having a raised fiber layer.

Among artificial leathers, the advantages are particularly exhibited in the case of artificial leathers made of fiber bundles with ultra-fine fineness, and the above-mentioned disadvantages can be solved.

That is, when the artificial leather obtained in the present invention is dyed with an acid dye, the polyurethane constituting the artificial leather is hardly dyed by the acid dye, and as a result, the polyester fiber entanglement and polyurethane are not dyed. There is no poor wash fastness as seen in disperse dye dyed artificial leather.

From this, the washing fastness of dyed artificial leather can be improved by using acid dyeable polyester fibers constituting artificial leather.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

In the examples, all parts indicating the amount added indicate parts by weight, and the intrinsic viscosity [η] is 50% of phenol/tetrachloroethane.
This is a value measured at 30°C in a solvent mixed at a weight ratio of :50.

Example 1 250 parts of dimethyl terephthalate, 240 parts of ethylene glycol, 0.118 parts of pentaerythritol, 0.05 part of zinc acetate, and 38 parts of the following amine compound (2.7 mol % based on dimethyl terephthalate) were charged into a reaction vessel. After continuing to heat and stir the mixture to 2 hours to carry out the transesterification reaction while removing by-produced methanol, 0.06 part of trimethyl phosphate and 0.10 part of germanium phosphite were added, and the temperature was gradually raised and the pressure was reduced to 270 °C. ℃
, 0.3 to 0.6 mmHg for 2 hours.

The obtained polymer was supplied to a pelletizer from a spinneret installed at the bottom of the reactor and taken out as chips.

This polyester is a pale yellowish white polyester chip with an intrinsic viscosity of 0.70.

This chip was spun using a composite spinneret with an island component and polyethylene as a sea component to give an island/sea component ratio of 50150. A 6 dr fiber was produced by water bath drawing, and after mechanical crimping, it was cut into a length of 503 m11. I got stable.

Using this stable, a random web was made according to a conventional method, and needle punching was performed using a No. 40 regular needle at a depth of 11 g under conditions of 700 times per square centimeter, and the weight was 1000. ! il/m2
A three-dimensional laminated nonwoven sheet was manufactured.

Next, the sheet was heat-treated under hot air at 110°C to heat-set and densify it, with an apparent density of about 0.301/13.
After immersing a prepolymer obtained by reacting 4,4'-diphenylmethane diisocyanate and polyethylene propylene adipate glycol in a 13% dimethylformamide solution of polyurethane obtained by chain extension with ethylene diamine, the impregnated polyurethane was wet-processed in water. It solidified.

Next, after extracting and removing the sea component in the fiber in hot toluene, it was sliced into two parts, and both sides were puffed with 120-mesh sandpaper to obtain an artificial leather original fabric with a raised fiber layer of thickness Q, 8 as. Ta.

This artificial leather was dyed with the bath composition shown below at a bath ratio of 50:l, a bath temperature of 120°C, for 90 minutes, and then a monoamine 1θ/11 bath ratio of 50:1, a bath temperature of 60°C, a time of 30 minutes. The /S value (calculated from Kuperkamunk's formula) of the dyed product obtained by washing thoroughly with water and drying is 1.
4.5, indicating excellent color development.

The washing fastness was measured according to JIS-L0844, No. A-2, and the results showed that it was grade 5 for discoloration and fading, and grade 5 for staining (attached white cloth).
Cotton), grade 4-5 (attached white cloth/nylon), and showed excellent wax fastness.

The exhaustion rate for artificial leather was 60%.

Next, dissolve the polyurethane from the dyed artificial leather in dimethylformamide, and use the colorimetric method to calculate the exhaustion rate of the acid dye to the polyurethane, which is approximately 10%.
Met.

On the other hand, the exhaustion rate of the polyester was about 80%, and it was dyed in a deep color.

Comparative Example 1 'Artificial leather was obtained in the same manner as in Example 1 using the polyester chips made without using the amine compound in Example 1.

This artificial leather was dyed using the same acid dye and under the same conditions as in Example 1.

The exhaustion rate for acidic dyes was 3%, and almost no dyeing was observed.

Comparative Example 2 The artificial leather used in Comparative Example 1 was dyed with a disperse dye in the bath composition shown below at a bath ratio of 50:1, a bath temperature of 120° C., and a time of 90 minutes.

Then hydrosulfide i i7i, caustic soda 1
1//lj, Amiradin (manufactured by Daiichi Kogyo Seiyaku ■) 11/i
t, bath ratio 50:1. The dyed product was subjected to reduction washing at a bath temperature of 80°C for 30 minutes, thoroughly rinsed with water, and dried. The /S value (calculated from the Kuperkamunk equation) was 13.2, showing good color development. .

However, when the washing fastness was measured using the same method as in Example 1, the results showed that the color change and fading were grade 3, and the staining was grade 1 (attached white cloth/cotton).
It was grade 1 (attached white cloth/nylon), which was extremely poor.

Example 2 225 parts of dimethyl terephthalate, 25 parts of dimethyl isophthalate, 240 parts of ethylene glycol, 0.53 parts of pentaerythritol, 0.05 part of zinc acetate, and 56 parts of the following amine compound (3 parts based on the acid component of the polyester) .0 mol%) into a reaction vessel, continue heating and stirring at 180°C, and carry out a transesterification reaction for 2 hours while removing by-product methanol, and then 0.06 part of trimethyl phosphate and 0.10 part of germanium phosphite are added. 260℃, 0.2~0.5m
The reaction was carried out at mHg for 2 hours.

The obtained polymer was supplied to a pelletizer from a spinneret installed at the bottom of the reactor and taken out as chips.

This polyester is a pale yellowish white polyester chip with an intrinsic viscosity of 0.65.

This chip is used as an island component and polyethylene is used as a sea component.
Spun with a sea component ratio of 50150 and 6d by water bath drawing method.
A fiber of R was produced, and after mechanical crimping treatment, it was cut into a length of 5Qmm to obtain a stable.

Using this stable, a random web was made according to a conventional method, and needle punching was performed using a No. 40 regular needle at a depth of 11 and 700 times per square centimeter. An entangled nonwoven sheet was produced.

Then, it was heat-treated under hot air at 115°C to make it heat-set and densified to have an apparent density of about 0.28θ/Cm3, and then immersed in a 13-polydimethylformamide solution of polyurethane with the same composition as used in Example 1. Dimethylformamide 30
% aqueous solution.

The sheet was further extracted and removed in hot toluene to remove polyethylene as a sea component in the fibers, and then sliced into two parts to obtain an artificial leather raw fabric.

This artificial leather was dyed with the bath composition shown below at a bath ratio of 50:l and a bath temperature of 110°C for 90 minutes. The dyed product obtained by soaping, thorough washing with water and drying had a /S value (calculated from the Kuperkamunk formula) of 13.5, and was dyed in a deep color.

The washing fastness was measured using the same method as in Example 1. Discoloration and fading were grade 5, staining was grade 5 (attached white cloth/cotton), and grade 5 (
(attached white cloth/nylon) and showed excellent firmness.

Comparative Example 4 Artificial leather was obtained in the same manner as in Example 2 using the polyester chips made without using the amine compound.

This artificial leather was dyed using the same acid dye and under the same conditions as in Example 2.

The exhaustion rate for acidic dyes was 4.0, and there was almost no dyeing.

Claims (1)

[Scope of Claims] 1. One or more compounds represented by the following formula (I) are added in a proportion of 0% to the acid component which is a constituent component of the polyester.
．． An artificial leather with improved dyeability, characterized in that it is composed of a fiber entangled body made of polyester fibers containing 5 to 20 moles of polyester fibers and a binder made of a polyurethane polymer. [However, R: an alkyl group, ", R": the same or different alkylene group having 3 to 8 carbon atoms, J, m: a value indicating the degree of polymerization of a polyoxyethylene group, with a relationship of 10≦, &+m≦300. It is a positive number that satisfies. ]