JP2972795B2 - Polyester fiber - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyester fiber comprising a polyester obtained by copolymerizing a polyorganosiloxane / polyester block copolymer.

(Prior art) Today, polyester produced industrially has high crystallinity, high softening point, and excellent properties such as strength, chemical resistance, heat resistance, weather resistance, and electrical insulation. It has been widely used for films, molded products, etc., including fiber applications, but in response to diversified applications in recent years, the demand for polyester fibers with various functionalities is increasing. It is just.

In particular, there are many demands for polyester fibers having properties such as water repellency and smoothness and feather-like feel (feather touch), and there has been a proposal to use polyester to impart such functionality to polyester fibers. Various things have been done.

One of the methods for obtaining water-repellent polyester fibers is to apply a treatment liquid containing a silicone (particularly polyorganosiloxane) -based water-repellent, oil-repellent and antistatic agent to the fiber (cloth) and heat-treat the fiber. is there.

Further, as a method for obtaining a polyester fiber having a feather-like feeling, smoothness, flexibility and elasticity, a method of adhering dimethylpolysiloxane to the polyester fiber has been adopted.

However, these methods have a problem that a special treatment step is required, the durability is not sufficient, and the effect is not durable.

In order to solve this problem, a method using an amino-modified polysiloxane as a treating agent or a method using a mixture of an amino-modified polysiloxane and an epoxy-modified polysiloxane as a treating agent are known. It is necessary to perform a heat treatment at a high temperature after the addition of the tar, so that there is a problem that the tared substance adheres to the processing apparatus, and the operability is poor due to the work required for cleaning and the like.

As a method of solving such a problem, a method of copolymerizing a polyorganosiloxane with a polyester can be considered, but it is difficult to copolymerize the polyorganosiloxane with a polyethylene terephthalate-based polyester as it is.

(Problems to be Solved by the Invention) The present invention is intended to solve the problem of the method of imparting functionality to such polyester fibers by surface treatment and to provide polyester fibers having functionality from the beginning. is there.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that it is easy to prepare a block copolymer in which polyorganosiloxane is previously copolymerized with a polylactone-based polyester. Can be copolymerized with polyethylene terephthalate-based polyester, and if the fiber is formed from polyester containing a specific amount of polysiloxane / polyester block copolymer having a specific molecular weight, water repellency, smoothness and feather-like texture The inventors have found that a polyester fiber having such functions as the above can be obtained, and have reached the present invention.

 That is, the present invention has the following configuration.

(1) Mainly an ethylene terephthalate unit, having a unit of the following formula and a unit having a weight ratio to the unit
Polyester fiber composed entirely of a polyester obtained by copolymerizing a polyorganosiloxane / polyester block copolymer having a molecular weight of 90/10 to 30/70 and a molecular weight of 600 to 40,000 to 1 to 40% by weight.

(Where m is 5 to 400, n is 2 to 400, p is 1 to 6, R ₁ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group having 6 to 20 carbon atoms, It is a group selected from alkenyl groups and acyl groups of the formulas 2 to 18.) (2) Mainly ethylene terephthalate units, units of the following formula and units of
A polyester fiber having a fiber surface portion composed of a polyester obtained by copolymerizing a polyorganosiloxane / polyester block copolymer having a molecular weight of from 90/10 to 30/70 and a molecular weight of from 600 to 40,000 to 1 to 40% by weight.

(Where m is 5 to 400, n is 2 to 400, p is 1 to 6, R ₁ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group having 6 to 20 carbon atoms, This is a group selected from alkenyl groups and acyl groups of Formulas 2 to 18.) Hereinafter, the present invention will be described in detail.

The polyester used in the present invention is a polyester mainly composed of ethylene terephthalate units and copolymerized with a polyorganosiloxane / polyester block copolymer (hereinafter simply referred to as a block copolymer).

The block copolymer in the present invention comprises a polyorganosiloxane block in the molecule and a polyester block obtained by ring-opening polymerization of a cyclic lactone, and can be produced by the following method.

(A) Ring-opening polymerization of a cyclic lactone directly to a modified polyorganosiloxane having an alcoholic hydroxyl group, and further, if necessary, acylating the terminal hydroxyl group with an organic carboxylic acid or an ester-forming derivative thereof or the like.

(B) Ring-opening polymers of mainly cyclic lactones, which have a reactive group such as a carboxyl group, a hydroxyl group or an ethylenically unsaturated double bond at the terminal, having a functional group which reacts with these reactive groups React with modified polyorganosiloxane.

Examples of the modified polyorganosiloxane used for producing the block copolymer include modified polyorganosiloxane having a Si-H bond and various modified compounds having a functional group bonded to a silicon atom of a polyorganosiloxane through an alkylene group. There are polyorganosiloxanes, more specifically, hydroxymethyl groups, hydroxyethyl groups,
Alcohol-modified polyorganosiloxane having hydroxypropyl group, etc., amino-modified polyorganosiloxane having aminoethyl group, aminopropyl group, etc., carboxylic acid-modified polyorganosiloxane having carboxyethyl, etc., mercapto-modified polyorgano having mercaptopropyl group, etc. Examples include siloxane and polyether-modified polyorganosiloxane having a polyether chain in the form of addition-polymerized alkylene oxide such as ethylene oxide or propion oxide to these functional groups. Among them, alcohol-modified polyorganosiloxane and carboxylic acid-modified polyorganosiloxane are preferred because of their easy production and excellent heat resistance per se.

On the other hand, examples of the lactone used for producing the block copolymer include β-propiolactone, δ-valerolactone, ε-caprolactone, etc. Among them, ε-caprolactone is preferred.

The block copolymer has a weight ratio of polyorganosiloxane block to polyester block of 90/10.
3030/70, preferably 70 / 30-40 / 60. If the ratio is out of this range, the reactivity of the obtained copolymer with the polyester becomes poor, and silicone oozes out on the fiber surface, which is not preferable.

A polyester block having a degree of polymerization of 2 to 400 is suitable. If the degree of polymerization is too high, it is difficult to uniformly copolymerize the block copolymer with the polyester. The polyorganosiloxane block preferably has a degree of polymerization of 5 to 400 (molecular weight of 500 to 35000). If the degree of polymerization is outside this range, the block copolymer cannot be uniformly copolymerized with the polyester. However, it is not preferable because functionalities such as water repellency and smoothness cannot be imparted to polyester.

In the present invention, the block copolymer is copolymerized with the polyester. The copolymerization amount must be 1 to 40% by weight, preferably 10 to 30% by weight, more preferably 15 to 30% by weight.
25% by weight is good. If the copolymerization amount is less than 1% by weight, the effect of imparting water repellency and feather-like feeling is insufficient. If it exceeds 40% by weight, the effect is not only saturated, but the melt viscosity becomes too high and the melting point becomes too high. In addition, spinning becomes difficult due to lowering, and the properties of the polyester fiber are impaired.

Next, a specific method for producing a polyester obtained by copolymerizing a block copolymer will be described.

First, a slurry of terephthalic acid (TPA) and ethylene glycol (EG) (TPA / EG molar ratio 1 / 1.2) was placed in an esterification reactor in which bis (β-hydroxyethyl) terephthalate and a low polymer (BHET) were present. ~ 1 / 1.8) continuously, under nitrogen gas control of 0.05 ~ 1.5Kg / cm ² G, 240 ℃ ~ 270 ℃
The esterification reaction is carried out at a temperature of
ET) is obtained continuously.

The resulting esterification product is transferred to a polymerization reactor, the required amount of block copolymer is added, and the polycondensation reaction is carried out at a temperature of 270 ° C to 290 ° C for 0.5 to 5 hours under a reduced pressure of 1 torr or less. Then, a polyester having a predetermined intrinsic viscosity is obtained.

The polycondensation reaction is usually performed in the presence of a polycondensation catalyst,
Examples of the polycondensation catalyst include compounds of metals such as antimony, germanium, tin, titanium, and cobalt commonly used in the production of polyesters, sulfosalicylic acid, o-
Organic sulfonic acid compounds such as sulfobenzoic anhydride are used. Incidentally, a polycondensation catalyst may be added in the esterification step.

The polyester fiber of the present invention can be obtained by spinning the polyester obtained by copolymerizing the block copolymer thus obtained by a conventional method.

The fibers of the present invention include fibers spun alone with polyester obtained by copolymerizing a block copolymer and fibers spun with another polymer such as polyethylene terephthalate so that the polyester forms a fiber surface portion (for example, , Sheath-core type composite fibers), and the cost can be reduced and the mechanical properties of the fibers can be increased without impairing the functionality.

The fiber of the present invention has functionalities such as water repellency and smoothness, and is widely used as a woven or knitted fabric, a nonwoven fabric, a wadding, or the like which requires these functionalities.

(Operation) The polyester fiber of the present invention, unlike the surface treated with a conventional silicone, is made of a polyester in which a polyorganosiloxane block is copolymerized, and thus has excellent washing resistance and dry cleaning resistance. ing.

(Examples) Hereinafter, the present invention will be described specifically with reference to examples.

The method for measuring and evaluating the characteristic values in the examples is as follows.
It is as follows.

Intrinsic viscosity [η] The viscosity was measured at 20 ° C using an equal weight mixture of phenol and ethane tetrachloride as a solvent.

Water repellency and smoothness were evaluated by the following tests.

(A) Water repellency test A water repellency test was conducted according to JIS L-1079 water repellency A method (spray method).

(B) Friction water repellency test A sample was rubbed 300 times under a load of 200 g using a Gakushin type friction fastness tester, and the water repellency of the rubbed portion was determined.

(C) Dry cleaning resistance test A dry cleaning cylinder is charged with 3.8 g of perchlorethylene at room temperature and 23 g of a sample, and treated for 30 minutes. Repeat this 10 times to check durability.

(D) Washing resistance test According to AATCC135-1970 II-B method.

The sample is placed in an automatic reversing type home washing machine containing 0.2% solution of a neutral detergent at 40 ° C, treated at a 1/50 bath ratio for 12 minutes, washed with water and dried. Repeat this 10 times to check durability.

(E) Smoothness test Smoothness was judged by tactile sensation. Compared with feather futon, ◎ was the best (equal to or more than feather futon), × was the worst, ◎, ○, △, × It was determined at the stage.

Reference Example 1 (Production example of block copolymer) In a reaction vessel under a nitrogen gas atmosphere, 15 kg of a modified polydimethylsiloxane having a hydroxypropyl group at both ends having a molecular weight of 8500 was charged, heated to 150 ° C, and stirred at 150 ° C. 15 kg of caprolactone were slowly added dropwise. After dropping, the mixture was aged at 160 ° C for 5 hours, cooled to 70 ° C, and added with 364 g of acetic anhydride.
Heated to 0 ° C.

The generated acetic acid was removed under reduced pressure to obtain a block copolymer having a molecular weight of 15,000.

Reference Examples 2 to 4 In the same manner as in Reference Example 1 using a modified polydimethylsiloxane having a molecular weight of 2,000, 4,500, 15,000, and 35,000 and having hydroxypropyl groups at both ends, the molecular weight was 4,500, 10,000, 30,000.
And 60,000 block copolymers.

Example 1 A slurry of TPA and EG (molar ratio: 1 / 1.6) was continuously supplied to an esterification reactor in which BHET was present, at a temperature of 250 ° C., a pressure of 0.05 kg / cm ² G, and a residence time of 8 hours. The BHET with an esterification reaction rate of 95% was continuously obtained.

50 kg of this BHET was transferred to a polymerization tank and heated to 280 ° C., and antimony trioxide was used as a catalyst at 2 × 10 ⁻⁴ per mole of TPA.
Mole and the block copolymer obtained in Reference Example 1 were added in an amount of 20% by weight based on the produced polyester. Thereafter, a polycondensation reaction was carried out at 280 ° C. and finally under a reduced pressure of 0.1 torr for 2.5 hours.
[Η] 0.63 polyester was obtained.

Using a spinneret having a pore size of 0.15 mm and 24 holes, the obtained polyester was used at a spinning temperature of 290 ° C, a discharge rate of 19 g / min, and a spinning speed of 2
Spinning was performed at 000 m / min.

The obtained undrawn yarn is drawn at a draw ratio such that the residual elongation becomes 30%, at a drawing temperature of 80 ° C, a drawing speed of 600 m / min, and a heat treatment temperature of 1
Polyester fiber was obtained by drawing heat treatment at 50 ° C.

Characteristics such as water repellency and smoothness of the obtained polyester fiber were measured.

The results are shown in Table 1. Examples 2 to 6 and Comparative Examples 1 to 4 The block copolymers of various molecular weights obtained in Reference Examples 1 to 4 were added in the amounts shown in Table 1, and And a polyester fiber was obtained.

However, in Comparative Example 2, the produced polyester could not be dispensed in a uniform strand form.
In this case, the polyester formed into a lump during the polycondensation reaction and could not be discharged, so that the polyester to be spun could not be obtained.

Characteristics such as water repellency and smoothness of the obtained polyester fiber were measured.

The results are shown in Table 1. Comparative Example 5 Using polyethylene terephthalate of [η] 0.71, yarn was formed under the same spinning conditions as in Example 1 to obtain polyester fibers.

Characteristics such as water repellency and smoothness of the obtained polyester fiber were measured.

The results are shown in Table 1. Comparative Example 6 In Example 1, a polyester was produced using a modified polydimethylsiloxane having a molecular weight of 15,000 and having hydroxypropyl groups at both ends instead of the block copolymer, and spinning was attempted. However, the modified polydimethylsiloxane was poorly dispersed, did not sufficiently copolymerize with the polyester, and was frequently broken, and could not be wound.

Example 7 The polyester of Example 1 was used as a sheath component, and polyethylene terephthalate of [η] 0.69 was used as a core component.
Using 265 spinnerets, sheath / core composite ratio 1/1, spinning temperature 290
The composite spinning was performed under the conditions of ° C, a discharge rate of 223 g / min, and a spinning speed of 1000 m / min.

The obtained undrawn yarn was drawn at a draw ratio of 2.8 at a drawing temperature of 80 ° C. and heat-set to obtain a conjugate fiber having a single yarn fineness of 3 denier.

When the properties of the obtained polyester composite fiber, such as water repellency and smoothness, were measured, the properties were equivalent to those of Example 1.

(Effects of the Invention) According to the present invention, a polyester fiber having excellent durability, such as water repellency and smoothness, is provided.

The fiber of the present invention can be produced with good operability since the block copolymer is well copolymerized with the polyester, and can be produced without requiring a special treatment step such as a surface treatment method. is there.

In addition, the fiber of the present invention exhibits good dyeability since its surface is not coated with a treatment liquid such as a water repellent.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D01F 6/84 301-6/86 307 D01F 8/14 C08G 63/695

Claims (2)

(57) [Claims] (1) Mainly comprising ethylene terephthalate unit,
A polyorganosiloxane / polyester block copolymer having a unit represented by the following formula and having a weight ratio to the unit of 90/10 to 30/70 and a molecular weight of 600 to 40,000:
Polyester fiber whose entire fiber is composed of up to 40% by weight of a copolymerized polyester. (Where m is 5 to 400, n is 2 to 400, p is 1 to 6, R ₁ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group having 6 to 20 carbon atoms, It is a group selected from alkenyl groups and acyl groups of Formulas 2 to 18.) 2. An ethylene terephthalate unit as a main component,
A polyorganosiloxane / polyester block copolymer having a unit represented by the following formula and having a weight ratio to the unit of 90/10 to 30/70 and a molecular weight of 600 to 40,000:
Polyester fiber whose fiber surface is composed of a polyester copolymerized to 40% by weight. (Where m is 5 to 400, n is 2 to 400, p is 1 to 6, R ₁ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group having 6 to 20 carbon atoms, It is a group selected from alkenyl groups and acyl groups of Formulas 2 to 18.)