JPH059367A - Acid dye-dyeable polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain an acid dye-dyeable polyester composition low in coloration of the polymer and excellent in light resistance, washing resistance, etc., by blending a specified quarternary phosphonium compound as a dyeing assistant. CONSTITUTION:A composition obtained by blending (A) 100 pts.wt. polyester composed of an aromatic dicarboxylic acid as the main acid component and an aliphatic and/or alicyclic diol as the main glycol component and having preferably >=0.3, especially 0.4-1 intrinsic viscosity with (B) 5X10<-4>-5X10<-2>mol, preferably 1X10<-3>-2X10<-2>mol compound of the formula (R1, R2, R3, R4, R5, R6, and R7 are 4-10C univalent hydrocarbon group, preferably phenyl; R4 is 4-16C divalent hydrocarbon group, preferably straight chain polymethylene group, etc.; X<-> is sulfonic acid anion, preferably methanesulfonic acid anion) synthesized, e.g. by reacting a diol compound with a sulfonic acid salt in the presence of a tertiary amine compound and then reacting a phosphine compound therewith at >=100 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyester composition dyeable with an acid dye. More specifically, the present invention relates to an acid dye-dyeable polyester composition containing a specific quaternary phosphonium compound as a dyeing agent.

[0002]

2. Description of the Related Art It is well known that polyesters, especially polyethylene terephthalate (hereinafter sometimes referred to as PET) have many excellent properties and are therefore used in a wide variety of applications.

However, in the use of fibers, if there is a polyester fiber which can be dyed with an acid dye, for example, a cloth is made of three kinds of fibers, that is, PET dyeable with cationic dye, ordinary PET and PET dyeable with acid dye. Make 1
Different colors can be dyed by different degrees of dyeing.
Further, when polyester fiber and wool are mixed-spun, various advantages can be obtained in various fields of application, such as dyeing with only an acid dye.

From such a point of view, various attempts have been made so far to impart dyeability to an acid dye to polyester. However, most of these are methods of copolymerizing or blending an amine compound, and thus the obtained polymer is liable to be colored and is inferior in light resistance, and thus has not yet been put into practical use. Is the reality.

As another method of obtaining a polyester dyeable with an acid dye, a method of blending a quaternary phosphonium compound is proposed in, for example, Japanese Patent Publication No. 44-302302. However, the polyester obtained by this method has dyeability even with a cationic dye if it is an acid dye only, so cationic dye dyeable PET, acidic dye dyeable P
Using ET and ordinary PET, it is not possible to dye three colors separately.

Further, in the publication, [R ₁ R ₂ R ₃ R
A method of blending a monoquaternary phosphonium compound represented by ₄ P] X is also disclosed.
Probably because of the low affinity between the high-grade phosphonium and the polyester, the resulting dyed product is inferior in sharpness, and the washing fastness (contamination resistance and dry cleaning resistance) is also low.

[0007]

DISCLOSURE OF THE INVENTION The present invention is intended to impart the ability of a polyester represented by PET to be dyeable with an acid dye and not dyeable with a cationic dye, and to reduce the coloring of a polymer. Moreover, it is intended to provide a polyester having excellent properties such as light resistance and washing resistance.

[0008]

The present inventors have found that among the quaternary phosphonium compounds, they are less colored even at a polyester melting temperature as high as 280 ° C., and are dyed only with acid dyes and are compatible with cationic dyes. As a result of examining various compounds having no property, the quaternary phosphonium base was found to be 1
The present invention has been completed by discovering that two specific phosphonium compounds present in the molecule are suitable for achieving the above object.

That is, according to the present invention, 100 parts by weight of a polyester having an aromatic dicarboxylic acid as a main acid component and an aliphatic diol and / or alicyclic diol as a main glycol component is added to the following general formula (I). ) The quaternary phosphonium compound represented by the formula (5) is 5 × 10 ^{−4 to} 5 × 10
^-Acid dye dyeable polyester composition characterized by being blended in ² mol,

[0010]

[Chemical 2] [However, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ are the same or different monovalent hydrocarbon groups having 4 to 10 carbon atoms, and R ₄ is 4 to 16 carbon atoms. divalent hydrocarbon group, X ^-
Represents a sulfonate anion. ] Is provided.

The polyester used in the present invention is a polyester containing an aromatic dicarboxylic acid as a main acid component and an aliphatic diol and / or an alicyclic diol as a main glycol component. It is a polymer obtained by subjecting an ester-forming derivative, an aliphatic diol and / or an alicyclic diol, and / or an ester-forming derivative thereof to a polycondensation reaction.

The aromatic dicarboxylic acid referred to here is
For example, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthretanedicarboxylic acid, 2,5-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 3,3′-diphenyldicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid, 4,4 '
-Diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 1,2-bis (phenoxy)
Examples thereof include ethane-4,4'-dicarboxylic acid, and among them, terephthalic acid is preferable.

Two or more of these aromatic dicarboxylic acids may be used in combination. If the amount is small, one or more of these aromatic dicarboxylic acids may be used together with adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Can be used together.

Examples of the aliphatic diol compound include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol and triethylene glycol. On the other hand, as the alicyclic diol compound, 1,
4-cyclohexanediol, 1,4-cyclohexane dimethanol, etc. can be illustrated. Among them, ethylene glycol or butylene glycol is particularly preferable. These glycol components can be used alone or in combination of two or more, and if a small amount, a polyoxyalkylene glycol whose both ends or one end is unblocked can be copolymerized with these diol compounds. ..

Further, polycarboxylic acids such as trimellitic acid and pyromellitic acid, and polyols such as glycerin, trimethylolpropane and pentaerythritol can be used within the range where the polyester is substantially linear.

The polyester is synthesized by any method. For example, polyethylene terephthalate is usually described by direct esterification reaction of terephthalic acid and ethylene glycol, transesterification of lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or terephthalic acid and ethylene oxide. Or the reaction of the first step to form a glycol ester of terephthalic acid and / or a low polymer thereof, and heating the reaction product of the first step under reduced pressure to a desired degree of polymerization. It is produced by the second stage reaction of condensation reaction.

In the polyester composition of the present invention,
The fourth represented by the following general formula (I) in the above polyester
It is necessary that a graded phosphonium compound is blended.

[0018]

[Chemical 3]

In the formula, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R
₇ represents a monovalent hydrocarbon group having 4 to 10 carbon atoms, and specific examples thereof include a phenyl group and a butyl group. Particularly, in the case of a phenyl group, dispersibility in polyester is improved and dyeing is performed. It is preferable because the sharpness is improved. When the number of carbon atoms in the hydrocarbon group is less than 4, not only the quaternary phosphonium compound is easily released during the dyeing treatment, but also the durability of the dyed product (contamination resistance, dry cleaning resistance, transfer resistance) (E.g., property) is not preferable. On the other hand, when it exceeds 10, the compatibility with polyester is lowered, the sharpness of the dyed cloth is lowered, and the weight of the quaternary phosphonium compound to be blended for dyeing at the same concentration is increased, It is not preferable because the moldability of the composition and the physical properties of the resulting molded article (such as fibril resistance and alkali resistance) are reduced.

R ₄ represents a hydrocarbon group having 4 to 16 carbon atoms, and particularly preferably a linear polymethylene group or a group in which a part of hydrogen is replaced with a methyl group. _{Specifically, - (CH 2) 4 -} , - (CH 2) 6 -, - (C
H ₂ ) ₁₀ −, − (CH ₂ ) ₁₂ −, − (CH ₂ ) ₁₆ −, −
_{CH 2 CH 2 CH (CH 3} ) CH 2 CH 2 - can be mentioned, in particular _{- (CH 2) 10 -,} - (CH 2) 12 - is preferable.

X represents a sulfonic acid residue represented by RSO ₃ −, and among them, methanesulfonic acid anion, p
-Toluenesulfonate anion is preferable, and in particular, methanesulfonate anion is preferable because the compatibility with polyester is improved and the sharpness of the dyed product is improved.

The quaternary phosphonium compound is produced, for example, as follows. That is, a diol compound such as hexanediol or decanediol is reacted with a sulfonic acid chloride such as paratoluenesulfonic acid chloride in the presence of a tertiary amine compound to form a disulfonic acid ester, and then a phosphine such as triphenylphosphine or tributylphosphine. It can be easily obtained by reacting with a compound at a temperature of 100 ° C. or higher.

The quaternary phosphonium compound preferably used is

[0024]

[Chemical 4] Etc., and these can be used alone, 2
You may use together 1 or more types. Among _{them, Ph 3 P (CH 2)} 10 PPh 3 · (CH 3 SO 3 -) 2 Ph 3 P (CH 2) 12 PPh 3 · (CH 3 SO 3 -) 2 is good compatibility with polyethylene terephthalate In addition, the heat resistance and the affinity with the acid dye are good, and thus a clear dyed product can be easily obtained, which is preferable.

The amount of the quaternary phosphonium compound added to the polyester is 5 × 10 ^{-4 to} 5 × 10 ^-2 mol, preferably 1 × 10 ^-3 to 100 parts by weight of the polyester.
It must be in the range of 2 × 10 ^-2 mol. The blending amount is 5
When the amount exceeds 10 ⁻² mol, the dyeability of the acid dye is saturated and no remarkable improvement can be obtained anymore, and the physical properties of the polyester are rather deteriorated. On the other hand, when the amount is less than 5 × 10 ⁻⁴ mol, the dyeability with an acid dye becomes insufficient and the object of the present invention cannot be achieved, which is not preferable.

The polyester can be blended with the quaternary phosphonium compound described above at any stage prior to molding the polyester. For example, it may be mixed into the polyester raw material before the start of the first-step reaction of the above-mentioned polyester synthesis, or may be added between the end of the first-step reaction and the start of the second-step reaction. It may be added during the two-step reaction. Further, the obtained polyester may be melt-added when it is formed into a fiber or the like. Above all, from the point that the time for which the quaternary phosphosnium compound is exposed to a high temperature atmosphere is shortened and the color tone of the resulting composition is improved, after the start of the second step reaction of the polyester synthesis reaction, especially the polyester It is desirable to add it after the intrinsic viscosity reaches 0.3 or more.

In the thus obtained polyester composition of the present invention, if the degree of polymerization of the polyester is too low, the mechanical properties of the molded product when formed into a molded product such as fiber will be insufficient, so that the intrinsic viscosity ( It is preferable that the value of (measured in orthochlorophenol under 35 ° C.) is 0.3 or more, and particularly 0.4 to 1.0.

The polyester composition of the present invention contains
If desired, any additives such as dyes, pigments, matting agents, anti-coloring agents, flame retardants, antioxidants, antistatic agents, and inorganic fine particles may be contained.

[0029]

EFFECTS OF THE INVENTION The acid dye dyeable polyester composition of the present invention is much less colored than those conventionally proposed, and can be dyed very beautifully by molding with an acid dye after molding into fibers or the like. it can. Further, the acid dye dyeing agent used in the present application has excellent affinity with polyester,
And it is presumed that it is excellent in affinity with an acid dye, but when dyeing nylon with an acid dye, a fixing treatment is usually performed after dyeing, whereas in the polyester composition of the present invention, It has the feature that it does not cause contamination (dye loss during washing, migration) even if it is not fixed.

The acid dye dyeing agent used in the present invention can be easily produced from a general-purpose raw material, and is excellent in heat resistance, and is melt-polymerized which is adopted for producing ordinary polyethylene terephthalate. Since there is very little coloring even under temperature conditions, there is also an advantage that a high-quality acidic dye-dyeable polyester composition can be obtained at low cost.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, the part in an Example shows a weight part. Moreover, each evaluation item was as follows.

Intrinsic viscosity [η] Dissolved in orthochlorophenol and measured at 35 ° C. using an Ostwald viscosity tube.

Polymer Color According to JIS Z8722.

Polymer haze value After placing 20 mg of polymer between two glass cover glasses for a microscope to heat and soften it on a hot plate at 280 ° C.,
A sample for measuring haze value (without air bubbles) is prepared by pressing and forming a circular shape with a diameter of about 10 mm, immediately putting it in ice water together with a cover glass and quenching. This sample was measured with the integrating sphere turbidimeter using the white plate method.

Dyeing rate The residual liquid after dyeing was determined by colorimetric determination.

Dyeing treatment The dyeing conditions with the acid dye were according to Table 1 below.

[0037]

[Table 1]

Lightfastness: The dyed cloth is irradiated with a xenon arc lamp, and from its discoloration and fading,
It was evaluated based on the blue scale.

Dyeing fastness (stain resistance) According to JIS L0846 A method.

Dyeing fastness (dry cleaning resistance) According to JIS L0860.

[0041]

[Reference Example] Synthesis Example of Quaternary Phosphonium Compound Decanediol and methanesulfonic acid chloride are reacted in pyridine, and the obtained reaction product is thoroughly washed with water, dried at low temperature, and then recrystallized from acetone to give the following formula. A disulfonic acid ester represented by CH ₃ —SO ₃ — (CH ₂ ) ₁₀ —O ₃ S—CH _{3 The} obtained disulfonic acid ester compound and triphenylphosphine were heated at 130 ° C. for 2 hours, and then at 160 ° C. for 30 hours.
The reaction was carried out separately to obtain a quaternary phosphonium compound shown below. ^{_{(Ph) 3 P + - (}} CH 2) 10 -P + (Ph) 3 · (CH 3 -SO 3 -) 2

[0042]

Example 1 A glass flask was charged with 100 parts of dimethyl terephthalate, 70 parts of ethylene glycol and 0.02 part of manganese acetate / tetrahydrate, and heated from 140 ° C. to 230 ° C. in a nitrogen gas atmosphere for 4 hours. The produced methanol was distilled out of the system to carry out a transesterification reaction. Phosphoric acid was added to the obtained reaction product in an amount of 0.02 part, and then antimony trioxide was added in an amount of 0.05 part to transfer the whole amount to a polymerization flask. Then, the reaction temperature was gradually raised from 230 ° C. to 275 ° C., and the pressure was gradually reduced from 760 mmHg to cause polycondensation, and the intrinsic viscosity of the polyester was adjusted to 0.
When it reached 3, 4.27 parts (5 × 10 ⁻³ mol per 100 parts by weight of the polyester obtained) of the quaternary phosphonium compound synthesized in Reference Example was added as an acid dye dyeing agent, and further added at 275 ° C. , 0.5 mmHg for 1 hour to react, intrinsic viscosity 0.6, polymer color L value 78, b value 2.3
A polymer having an extremely good whiteness was obtained.

The obtained polymer was formed into chips, and then melt-spun (spinning temperature 280 ° C.) according to a conventional method to obtain an unstretched yarn, which was stretched 4.5 times to 75 denier / 2.
A multifilament of 4 filaments was obtained.

When this drawn yarn was knitted after knitting and dyed under the above dyeing conditions, the dyeing rate was 100%, and the acid dyeability was very good. The evaluation results of the obtained dyed cloth are shown in Table 2.

A cationic dye (Aizen Cathilon Pink FGH 2% owf) was used in place of the acid dye to obtain 130
It was dyed for 1 hour at 0 ° C., but it was dyed only to the extent of contamination and was not dyed substantially.

[0046]

[Examples 2 to 7 and Comparative Examples 1 to 3] Fourth Example used in Example 1
The same as Example 1 except that the quaternary phosphonium compound shown in Table 2 is used instead of the primary phosphonium compound (however, Comparative Examples 1 to 3 are added in a 2-fold molar amount to make the amounts of the phosphonium cation groups equal). The results obtained in Table 2
Shown in.

[0047]

[Table 2] The quaternary phosphonium compounds a to n in the table are shown below. A: Ph ₃ P (CH ₂ ) ₁₀ PPh ₃ · (OMs) ₂ b: Ph ₃ P (CH ₂ ) ₁₀ PPh ₃ · (OTs) ₂ c: Bu ₃ P (CH ₂ ) ₁₀ PBu ₃ · (OMs) ₂ d: Ph ₃ P (CH ₂ ) ₁₂ PPh ₃ · (OMs) ₂ e: Bu ₃ P (CH ₂ ) ₆ PBu ₃ · (OMs) ₂ f: Ph ₃ P (CH ₂ ) ₄ PPh ₃ · (OTs ) _{2 To} : Ph ₃ P (CH ₂ ) ₁₆ PPh ₃ · (OTs) ₂ Chi: Ph ₄ P · Cl Re: Ph ₃ PCH ₃ · (OTs) Nu: Ph ₃ P (CH ₂ ) ₁₇ CH ₃ · ( (OMs) (However, OMs is a methanesulfonic acid residue and OTs is a paratoluenesulfonic acid residue.)

Claims (1)

Claims: 1. An aromatic dicarboxylic acid as a main acid component,
With respect to 100 parts by weight of polyester containing an aliphatic diol and / or alicyclic diol as a main glycol component,
An acidic dye-dyeable polyester composition comprising a quaternary phosphonium compound represented by the following general formula (I) in an amount of 5 × 10 ^{−4 to} 5 × 10 ⁻² mol. [Chemical 1] [However, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ are the same or different monovalent hydrocarbon groups having 4 to 10 carbon atoms, and R ₄ is 4 to 16 carbon atoms. divalent hydrocarbon group, X ^-
Represents a sulfonate anion. ]