JP3224309B2 - Polyester fiber with improved room temperature soil release - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an antifouling polyester, and more particularly to a polyester fiber having improved room temperature soil release.

[0002]

2. Description of the Related Art Polyester fibers have excellent dimensional stability,
Because of its excellent properties, such as being strong and resistant to wrinkling, it is used in all fields of clothing. In particular, in hospital clinics, food industries, offices, and the like, various uniforms have recently been used, and there has been remarkable development of polyester fibers in the field of textile uniforms. However, polyester fibers having such excellent properties are also extremely poor in water absorption and moisture absorption due to their hydrophobicity, and are more easily adhered to oily stains than hydrophilic fibers such as cotton. Has a problem that it is easily recontaminated. This is a problem that has always been raised since the development of polyester fibers in the field of textile uniforms, and many methods have been proposed to solve this problem.

[0003] Among them, the inventors of the present invention have proposed a polyoxyethylene polyether obtained by copolymerizing ethylene oxide with a specific olefin oxide and making it water-insoluble, and blending the resulting composition with an antifouling composition. Was found to be significantly improved (Japanese Patent Laid-Open No. 2-269).
762, JP-A-3-182546). However, in this method, since the polyether is merely physically dispersed in the polyester, the washing durability is limited.

On the other hand, as a method for imparting hydrophilicity to polyester, a method of copolymerizing a polyoxyethylene-based polyether with the polyester is known. For example, polyoxyethylene glycol phenyl glycidyl ether (JP-A-1-236236) or It is disclosed that by copolymerizing polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether (JP-A-1-234420), a polyester excellent in water absorption and sweat absorption can be obtained. According to this method, excellent antifouling property can be imparted with sufficient washing durability as compared with regular products.

[0005] However, all polyester fibers obtained by the above-mentioned technique show excellent soil release properties when washed in warm water at 40 ° C specified by the JIS evaluation method, but are generally used at home in practice. It was found that there was a problem that the soil release property was not sufficiently exhibited when washing with tap water at normal temperature.

In order to impart higher hydrophilicity to polyesters, the present inventors have known alkali metal salts of ω-hydroxypolyalkylenebenzenesulfonic acid and ω-hydroxypolyalkylenecresol sulfone, which are known as polyethers having sulfonic acid groups. The acid alkali metal salt (GB868150) was copolymerized with polyester, and the soil release property was evaluated. However, these modifiers are originally intended to improve the dyeing properties, and as in the above-mentioned technology, the soil release properties in room temperature water were insufficient.

[0007]

Accordingly, the present inventors have developed an excellent soil release property when washing not only with hot water at 40 ° C. but also with normal temperature water (here, 10 ° C. for convenience) used for washing at home. As a result of intensive studies for the purpose of providing a polyester fiber having the following, the present invention has been achieved.

[0008]

That is, the present invention provides a compound represented by the following general formula (I) at least at a part of a polyester terminal having ethylene terephthalate as a main structural unit.

[0009]

Embedded image

Wherein M is a hydrogen atom, a monovalent metal or a quaternary phosphonium salt. R ¹ is a hydrocarbon group having 1 to 25 carbon atoms, and R ² is a hydrocarbon group having 1 to 21 carbon atoms. P is an integer of 0 to 4, q is an integer of 1 to 5, and p + q ≤ 5. Here, when p is an integer of 2 to 5, R ¹ is the same. Or different.
m and n are each —CH ₂ CH ₂ O—,

[0011]

Embedded image

It represents the number of moles of each component, and each component exists as a random or block copolymer with each other. m is an integer of 15 to 100, n is an integer of 1 to 50, m
+ N is an integer of 20 to 100. ) A polyester obtained by copolymerizing a polyoxyalkylene-based polyether having a molecular weight of 6000 or less, the amount of which is 0.5 to 10% by weight based on the weight of the matrix polyester. It is a polyester fiber having properties.

The polyoxyalkylene-based polyether used in the present invention (hereinafter referred to as polyether).
Is represented by the above formula (I).

In the formula, M is a hydrogen atom, a monovalent metal or a quaternary phosphonium salt. Na as a monovalent metal,
Li, K, Ca, Mg, Al and the like.
K, Li, and Ca are preferred. In the case of a quaternary phosphonium salt, it is represented by PR ³ R ⁴ R ⁵ R ⁶ , and R ³ , R ⁴ , R
⁵ or R ⁶ may be the same or different groups selected from an alkyl group and an aryl group.

R ¹ is a hydrocarbon group having 1 to 25 carbon atoms. As the hydrocarbon group, an alkyl group is preferable, and among them, an alkyl group having 1 to 14 carbon atoms is preferable.

R ² is a hydrocarbon group having 1 to 21 carbon atoms. The hydrocarbon group may be an alkyl group or an aryl group, and may be a combination of two or more types. Among them, an alkyl group having 1 to 21 carbon atoms is preferable. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, a dodecyl group, and a henicosan group.

P is an integer from 0 to 4, q is a positive integer from 1 to 5, and p and q satisfy p + q ≦ 5. p is preferably 0, 1 or 2, and q is preferably 1 or 2. When p is an integer of 2 to 4, R ¹ may be the same or different. The substitution positions of the sulfonic acid group and R ^{1 on} the phenoxy group may be any positions. m and n are each —CH ₂ CH ₂ O—,

[0018]

Embedded image

Represents the number of moles of each component, and each component can have an arbitrary arrangement with each other and can be randomly copolymerized.
It may be a block copolymer or a combination thereof.

An integer, n is an integer of 1 to 50, and m + n is 20
It is an integer of １００100. If an attempt is made to copolymerize a polyester with a polyether having m + n of less than 20, a large amount of the polyether is required to obtain a sufficient soil release property. In such a case, the polyester itself is blocked because the end of the polyester is blocked. Cannot sufficiently increase the degree of polymerization, and the mechanical properties of the resulting fiber cannot be secured. On the other hand, when m + n is larger than 100, the reaction between the polyether and the polyester does not proceed sufficiently, and eventually the result is the same as that obtained by mixing and dispersing the polyether into the polyester, so that high washing durability cannot be maintained. In addition,
The polyether used in the present invention has a molecular weight of 60
00 or less, preferably 5000 or less, particularly preferably 4 or less.
500 or less.

The composition ratio of m and n is 0.01 ≦ n / m
≦ 1 is preferred. When the n / m is less than 0.01, the soil release property of the finally obtained polyester in normal temperature water does not exhibit a remarkable effect as compared with the conventional hydrophilic polyester. On the other hand, if n / m exceeds 1, the hydrophilicity of the polyether is reduced, so that the soil release property of oily soil is rather poor.

The characteristics of the above compounds are that they have a sulfonic acid group at the end of the polyether chain and have

[0023]

Embedded image

The unit represented by the formula (1) is introduced. Surprisingly, by using a polyether having this structure, the soil release property in not only warm water but also normal temperature water can be remarkably improved.

The polyether represented by the formula (I) can be easily produced by subjecting ethylene oxide and / or alkylene oxide to ring-opening polymerization at an elevated temperature and pressure using a phenoxide having a suitable substituted sulfonic acid group. Can be. It is known that this polymerization process proceeds in a stepwise manner, and it is possible to produce a polyether having a molecular weight and a monomer sequence according to the purpose by adjusting the kind, composition and charge amount of the alkylene oxide at any stage. Is also possible. The molecular weight of the produced polyether can be easily determined by quantifying the terminal hydroxyl group.

In the present invention, the polyester for copolymerizing the above polyether is a polyester containing terephthalic acid as a main acid component and ethylene glycol as a main glycol component. In such a polyester, a part of terephthalic acid which is an acid component thereof may be replaced with another difunctional carboxylic acid. Such other carboxylic acids include, for example, isophthalic acid, 5-sodium sulfoisophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-oxyethoxybenzoic acid, and p-oxybenzoic acid. Examples thereof include functional aromatic carboxylic acids, difunctional aliphatic carboxylic acids such as sebacic acid, adipic acid and oxalic acid. Further, a part of the ethylene glycol component may be replaced by another glycol component. Examples of such a glycol component include trimethylene glycol, tetramethylene glycol, pentamethylene glycol,
Hexamethylene glycol and the like, and other diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, bisphenol A, aliphatic, alicyclic and aromatic diol compounds such as bisphenol S;
Examples include polyoxyalkylene glycols whose both ends are unblocked.

Such a polyester can be produced by any method. For example, if polyethylene terephthalate is explained, terephthalic acid and ethylene glycol are directly esterified, terephthalic acid lower alkyl ester such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are reacted. The first-stage reaction of reacting with an oxide to form a glycol ester of terephthalic acid and / or a low polymer thereof, and then heating the product under reduced pressure to obtain a polycondensation reaction until a desired degree of polymerization is reached. Easily produced by the second stage reaction.

In order to copolymerize the above-mentioned one-end-blocked polyether at the end of the polyester chain, any step before the completion of the above-mentioned synthesis of the polyester, for example, before the start of the first step, during the reaction, or at the end of the reaction Thereafter, it may be added at an arbitrary stage such as during the second stage reaction, and the production reaction may be completed after the addition.

If the amount of the polyether used at this time is too small, the soil release property of the finally obtained polyester fiber and the washing durability thereof become insufficient. Since the degree of polymerization reaches a peak at a low level, the yarn properties such as the strength of the finally obtained polyester fiber deteriorate. Also, when it comes to contain a large amount of polyether,
Since the light resistance of the obtained fiber deteriorates, it is desirable that the copolymerization amount be as small as possible. In the present invention, the copolymerization amount of the polyether is 0.5 to 10 with respect to the polyester.
% By weight, especially in the range from 2 to 5% by weight. Thus, in the present invention, the copolymerization amount of the polyether can be suppressed to a small amount, so that the obtained fiber can also maintain sufficient light resistance.

If necessary, stabilizers, matting agents, antioxidants, fluorescent brighteners, catalysts, coloring inhibitors, heat-resistant agents, coloring agents, inorganic particles and the like may be used in combination. In particular, when the polyether is left at a high temperature such as melt spinning conditions, it is easily oxidized and problems such as a decrease in the degree of polymerization and coloring are likely to occur. Therefore, it is preferable to use an antioxidant or an optical brightener in combination. Often. Further, the polyester having a normal temperature soil release property in the present invention can be easily used in combination with other additional functions.For example, if an ionic antistatic agent is used in combination, it is possible to obtain a fiber having excellent antistatic properties. The field of application will further increase.

The degree of polymerization of the thus obtained polyester of the present invention is preferably 0.58 or more, more preferably 0.6 or more, in terms of intrinsic viscosity in order to exhibit sufficient fiber properties.

When fiberizing such a modified polyester, it is not necessary to employ a special method, and a melt spinning method of polyester fiber can be employed under arbitrary conditions. For example, a method of melt-spinning at a speed of 500 to 2500 m / min, stretching and heat treatment, a method of melt-spinning at a speed of 1500 to 5000 m / min and performing stretching and false twisting simultaneously or successively, 5000 m / min or more Arbitrary spinning conditions such as a method of melt-spinning at a high speed and omitting the stretching step depending on the application are adopted. Here, the fiber to be spun may be a solid fiber having no hollow portion or a hollow fiber having a hollow portion. Further, the outer shape and the shape of the hollow portion in the cross section of the fiber to be spun may be circular or irregular.

The spun fiber preferably has an elongation of 40% or less and a strength of 4 g / m 2 to exhibit sufficient fiber performance.
It is stretched so as to be not less than de and heat-treated as necessary.

[0034]

The reason why such an excellent low-temperature antifouling effect is exhibited is not yet clear, but the hydrophilicity and glass transition temperature of the polyether, the terminal group effect, the microphase of the polyether segment in the polyester fiber, and the like. It is considered that the separation state, the affinity of the polyester matrix with the polyether segment, the decomposability of the polyether segment with the washing water, and the like are complicatedly involved.

[0035]

When the polyester fiber of the present invention is made into a garment having a high washing frequency such as a uniform, for example, its characteristics are particularly exhibited, and the washing process is repeated severely.
In particular, it exhibits excellent durability and antifouling properties even in washing using low-temperature water of 20 ° C. or lower. Therefore, the polyester fiber of the present invention is extremely useful in the field of textile uniform. Application to the linen supply field is also effective.

Further, the polyester fiber of the present invention is used for blending, cross-weaving and the like with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and synthetic fibers other than the polyester of the present invention, if necessary.

[0037]

The present invention will be further described with reference to the following examples. Parts and% in Examples are parts by weight and% by weight, respectively. The intrinsic viscosity [η] of the polymer was found to be 0.62 to 0.70 in any of the examples as a result of determination from a value measured with an orthochlorophenol solution at 35 ° C.

In the examples, the following methods were employed for the washing treatment, the stain treatment, and the method of obtaining the stain rate.

(1) Washing treatment Water at a liquid temperature of 10 ° C. was put into a home washing machine, and a synthetic detergent for clothing was added thereto at a ratio of 2 g per 1 liter of water to be dissolved to prepare a washing liquid. A sample and a load cloth were added to the washing liquid so that the bath ratio was 1:30, and the operation was started. 5
After treatment for 0 minutes, the operation was stopped, and the sample and the load cloth were dehydrated by a dehydrator, and then subjected to overflow water washing for 15 minutes to dehydrate. The above washing was designated as LL5, and this was repeated the required number of times.

(2) Contamination treatment 10 cm ×
A 13 cm woven fabric was immersed and stained. Artificial stain liquid ・ Motor oil 99.335% by weight (Dia Queen Motor Oil M-2) manufactured by Mitsubishi Motors Corporation ・ C heavy oil 0.634% by weight ・ Carbon black 0.031% by weight Of contaminated liquid,
It was left at 80 ° C. for 8 hours in a dryer. This contaminated sample contains 2 g / l of Marcel soap under the weak conditions of a home washing machine.
Washed in water at 200C for 20 minutes. Then, the soil release property was evaluated by the following method.

(3) Evaluation of Soil Release Property Using a Minolta colorimeter CR-200 (Minolta Camera Sales Co., Ltd.), a CIE colorimeter ΔE of the sample was obtained by a conventional method.
^* Was determined, and the soil release property was calculated by the following equation.

[0042]

(Equation 1)

In the above formula, ΔE ^* : soil release property L ₁ , a ₁ , b ₁ : E ^* (L ^* , a ^* ,
b ^* ) L ₂ , a ₂ , b ₂ : E ^* (L ^* , a ^* ,
b ^* )

[0044]

Example 1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.066 mol% based on dimethyl terephthalate) and 0.1% of cobalt acetate tetrahydrate as a color-matching agent. 009 parts (0.007 mol% based on dimethyl terephthalate) were charged into a transesterification reactor, and the reaction product was heated from 140 ° C. to 220 ° C. over 4 hours under a nitrogen gas atmosphere, and was placed in the reactor. The transesterification reaction was performed while distilling off the generated methanol out of the system. After completion of the transesterification, 0.058 parts of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) and 0.024 parts of dimethylpolysiloxane as an antifoaming agent were added to the reaction mixture.
Next, 10 minutes later, 0.04 parts of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added to the reaction mixture, and the temperature was raised to 240 ° C. while simultaneously distilling off excess ethylene glycol. Thereafter, the reaction product was transferred to a polymerization reactor. Next, the following chemical formula was added to the reaction mixture.

[0045]

Embedded image

4 parts of a polyether having an average molecular weight of 2480 represented by (m is an average of 48 and n is an average of 4) are added, and the pressure in the reaction vessel is reduced from 760 mmHg to 1 mmHg over 1 hour. The temperature of the reaction mixture is 24
The temperature was raised from 0 ° C to 285 ° C. Polymerization was further performed under a reduced pressure of 1 mmHg. At this stage, Sumireizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and ADK STAB AO-412S (manufactured by Asahi Denka Co., Ltd.) were added to the reaction mixture as antioxidants for 0.2 times each. The polymerization was continued until the melt viscosity of the system reached a predetermined value. The obtained polymer was formed into chips by a conventional method.

After drying the obtained chip by a conventional method,
It is melted at 285 ° C. using an extrusion spinning machine having a spinneret having 24 circular spinning holes having a hole diameter of 0.3 mm, and a discharge amount of 3
The fiber is spun at 7.5 g / min at a take-up speed of 1500 m / min, and the obtained undrawn yarn is subjected to a drawing treatment machine having a heating roller at 80 ° C. and a plate heater at 160 ° C. to have an elongation of 30%. Stretch heat treatment at a draw ratio such that
A 5 denier / 24 filament drawn yarn was obtained.

A knitted fabric is manufactured using the obtained drawn yarn, and the knitted fabric is scoured by a conventional method and preset (180 ° C. ×
1 minute) to obtain a knitted fabric. This was subjected to the above-mentioned contamination treatment, and the stain removal property was evaluated.

FIG. 1 shows the results.

[0050]

Examples 2 to 10 The same operation as in Example 1 was performed. However, as a polyether, the following chemical formula

[0051]

Embedded image

The polyethers shown in Table 1 were used.

FIG. 1 shows the results.

[0054]

Example 11 The same operation as in Example 1 was performed. However, as a polyether, the following chemical formula

[0055]

Embedded image

(Wherein m is an average of 35 and n is an average of 10). A polyether having an average molecular weight of 2360 was used.

FIG. 1 shows the results.

[0058]

Comparative Examples 1 and 2 The same operation as in Example 1 was performed. However, instead of polyether, the following chemical formula

[0059]

Embedded image

Further, the polyoxyalkylene polyethers shown in Table 1 were used.

FIG. 1 shows the results.

[0062]

Comparative Example 3 The same operation as in Example 1 was performed. However,
Instead of polyether, a polyether having one end capped with an average molecular weight of 2500 represented by the following chemical formula C ₆ H ₅ O— (CH ₂ CH ₂ O) _m —H (where m is an average of 55) Oxyethylene-based polyether was used.

FIG. 1 shows the results.

[0064]

[Table 1]

[Brief description of the drawings]

FIG. 1 shows the soil release property when washed with a washing liquid at 10 ° C.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D01F 6/84 301-6/86 307 C08G 63/672

Claims (1)

(57) [Claims] 1. At least a part of a polyester having ethylene terephthalate as a main structural unit is represented by the following general formula (I): (Wherein, M is a hydrogen atom, a monovalent metal or a quaternary phosphonium salt. R ¹ is a hydrocarbon group having 1 to 25 carbon atoms, and R ² is a hydrocarbon group having 1 to 21 carbon atoms. P is an integer of 0 to 4, q is an integer of 1 to 5, p + q
≦ 5. Here, when p is an integer of 2 to 5, R ¹
May be the same or different. m and n are each —CH ₂ CH ₂ O—, It represents the number of moles of each component, and each component exists as a random or block copolymer with each other. m is 15
An integer of 100, n is an integer of 1 to 50, and m + n is 20 to
It is an integer of 100. A polyester copolymerized with a polyoxyalkylene-based polyether having a molecular weight of 6000 or less represented by the formula (1), wherein the copolymerization amount is 0.5 to 10% by weight with respect to the polyester as a matrix. Polyester fiber with properties.