JPH07138811A - Fiber made of block copolymer - Google Patents

Abstract

(57) [Summary] [Structure] Number average molecular weight consisting of vinyl aromatic monomers
Fibers, yarns and yarns produced using a block copolymer having a number average molecular weight of 20,000 to 500,000 consisting of a polymer block (A) of 2,500 to 400,000 and isobutylene and having a number average molecular weight of 10,000 to 400,000 (B). Cloth. [Effects] The fiber, yarn and cloth of the present invention have excellent stretchability, elastic recovery, vibration damping performance (vibration absorbing ability), noise prevention, weather resistance, heat aging resistance, etc. , Flooring materials, interior materials for homes that require noise absorption and vibration absorption of carpet bases, cushioning materials, sports clothing, stockings and socks, foundations, base materials for poultices,
It can be effectively used for a wide range of applications such as bandages, and since it has no double bond in the polymer molecule, it has excellent weather resistance, heat resistance, and heat aging resistance, and is resistant to discoloration and yellowing and good for a long time. The appearance and color tone can be maintained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber, a yarn and a cloth obtained by using a block copolymer composed of a polymer block composed of a vinyl aromatic monomer and a polymer block composed of isobutylene. Invention fiber,
Yarn and fabric have excellent elasticity, elastic recovery, vibration damping (vibration absorption), noise prevention, weather resistance, and heat aging resistance, and are effectively used in a wide range of applications. be able to.

[0002]

2. Description of the Related Art In recent years, there has been a great demand for quietness along with changes in lifestyle, and it has been designed for wall materials, floor materials, carpets with vibration damping performance (vibration absorption capacity) and noise prevention capacity. Interior materials for houses such as wood are required. As the interior material made of synthetic fibers having such characteristics, synthetic fibers are arranged in the length and width directions, and laminated and laminated to define the arrangement ratio (Japanese Patent Publication No. 55-42175), polyethylene terephthalate fiber. There is known a non-woven fabric which has been unstretched and then heat-shrinked to have a dense structure (Japanese Patent Laid-Open No. 60-199958).
However, in both cases, the polymer itself that constitutes the fiber does not have vibration damping performance (vibration absorbing ability), and therefore its noise prevention ability and sound absorbing ability are not sufficient.

Further, the mechanical loss factor (tan) is increased by increasing the proportion of 1,2- or 3,4-bonds in the polymer.
Hydrogenated isoprene-styrene block copolymers or butadiene-styrene block copolymers having an increased δ) have been proposed (JP-A-5-51823), and these block copolymers have a mechanical loss coefficient (tan δ). ) Is large, the vibration damping property is excellent, but since the double bond in the molecule does not completely disappear due to hydrogenation and remains, the weather resistance and heat aging resistance are not sufficient and yellowing occurs. It also has the drawback of fading easily.

Various stretch fibers and cloths using the stretch fibers have been heretofore known. Bandages, poultice base cloths, sports clothing, stockings, socks, foundations, etc. have been made use of their stretchability and elastic recovery. It is used in various applications such as cushioning cotton. In particular, a non-woven fabric made of polyurethane fibers (for example, JP-A-59-2
No. 23347) is excellent in stretchability and is used for the above-mentioned applications, but it is inferior in weather resistance and easily yellows,
It has drawbacks such as not being particularly suitable as a poultice base fabric due to its high modulus and coarse texture.

In order to avoid the above disadvantages of polyurethane,
Hydrogenated products of isoprene-styrene block copolymers have been proposed (Japanese Patent Laid-Open No. 4-11059), and although they are superior to polyurethanes, they have weather resistance because double bonds still remain in the molecule. It does not have sufficient properties and cannot completely avoid yellowing and fading during use.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to have a high elasticity and a high elastic recovery property, and a vibration damping property (vibration absorbing property).
Excellent in sound absorption and noise prevention, and also excellent in weather resistance and heat aging resistance, and is unlikely to cause yellowing, discoloration, heat deterioration, etc. Houses such as wall materials, floor materials, carpet base materials Interior materials, bandages, poultice base cloth, sports clothing,
Stockings, socks, underwear (foundation),
It is an object of the present invention to provide fibers, yarns, and cloths that can be effectively used in a wide range of applications such as cushioning cotton.

[0007]

As a result of continuous research by the present inventors in order to achieve the above object, a specific number average molecular weight of a polymer block composed of a vinyl aromatic monomer and a polymer block composed of isobutylene is obtained. The present invention has been completed based on the finding that the use of a block copolymer having ## STR4 ## yields fibers, yarns, and cloths having the various excellent properties described above.

That is, the present invention relates to a polymer block (A) made of a vinyl aromatic monomer and having a number average molecular weight of 2,500 to 400,000 (hereinafter simply referred to as "polymer block (A)").
1) and isobutylene having a number average molecular weight of 1
A block copolymer having a number average molecular weight of 20,000 to 500,000 (hereinafter referred to as "A / B block", composed of 30,000 to 400,000 polymer blocks (B) (hereinafter simply referred to as "polymer block (B)"). Fibers referred to as "copolymers"). The present invention further includes yarns and fabrics produced using the above fibers.

The fiber of the present invention is a polymer block as described above.
It is produced using an A / B block copolymer consisting of (A) and a polymer block (B). In that case, the polymer block
The vinyl aromatic monomer constituting (A) may be any cationically polymerizable vinyl aromatic monomer, and specific examples thereof include styrene, α-methylstyrene,
1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4
-Benzylstyrene, 4- (phenylbutyl) styrene, monochlorostyrene, dichlorostyrene, methoxystyrene, indene, acenaphthylene, etc. can be mentioned, and one or more of these vinyl aromatic monomers can be used. . Of these, the polymer block (A) is most preferably composed of styrene.

Further, the polymer block (A) needs to have a number average molecular weight of 2,500 to 400,000, more preferably 4,000 to 300,000. When the number average molecular weight of the polymer block (A) is less than 2,500, mechanical properties such as tensile strength as a fiber are deteriorated, while when it exceeds 400,000, the A / B block copolymer melts. Viscosity becomes too high, spinning becomes difficult, processability deteriorates, and fiber flexibility decreases.

The polymer block (B) is composed of isobutylene and has a number average molecular weight of 10,000 to 40.
It must be 10,000. Polymer block
When the number average molecular weight of (B) is less than 10,000, the flexibility of the block copolymer and fibers obtained therefrom is lost, while when it exceeds 400,000, the fluidity of the A / B block copolymer is reduced. And the spinning becomes difficult.

The number average molecular weight of the A / B block copolymer consisting of the polymer block (A) and the polymer block (B) must be 20,000 to 500,000. The number average molecular weight of the A / B block copolymer is 20,
If it is less than 000, the mechanical properties will be deteriorated and the strength will be lowered when it is made into fibers. On the other hand, if it exceeds 500,000, the melt viscosity will be too high and spinning will be difficult and the processability will be lowered, and the fiber will be soft. Lost sex.

The ratio of the polymer block (A) to the polymer block (B) in the A / B block copolymer is determined by the number average molecular weight of the block copolymer, the polymer block (A) and the polymer block (B). Generally, the polymer block (A) content is 5 to 80% by weight based on the weight of the A / B block copolymer.
The proportion of (B) is preferably 95 to 20% by weight, and the polymer block (A) is 10 to 70% by weight.
More preferably, (B) is 90 to 30% by weight. When the proportion of the polymer block (A) is less than 5% by weight [when the proportion of the polymer block (B) exceeds 95% by weight], A / B
When the mechanical properties of the block copolymer become insufficient, while the proportion of the polymer block (A) exceeds 80% by weight [when the proportion of the polymer block (B) is less than 20% by weight], the melt viscosity is It becomes high and spinning becomes difficult.

The A / B block copolymer may be linear or branched in two or more,
Further, the structure is not particularly limited as long as it has at least one polymer block (A) and at least one polymer block (B) in the molecule. Although not limited thereto, a typical example of the A / B block copolymer is the following formula (I) or formula (II):

[0015]

Embedded image Q- {C (R ¹ ) (R ² )-(BA) m} n (I)

[0016]

Embedded image Q- {C (R ¹ ) (R ² )-(AB) m} n (II) [In the formulas (I) and (II), Q is an n-valent hydrocarbon group, A is a polymer block (A), B is a polymer block
(B), R ¹ and R ² represent an alkyl group or an aralkyl group having 1 to 20 carbon atoms, m and n represent an integer of 1 or more, and m
Is preferably 1. ] What is represented by these can be mentioned.

The method for producing the A / B block copolymer is not particularly limited. For example, it can be produced by sequentially polymerizing a vinyl aromatic monomer and isobutylene in an inert solvent using a suitable polymerization initiator system. it can. An example of the polymerization initiator system in that case is a mixed system of a Lewis acid and an organic compound which produces a cationic polymerization active species by the Lewis acid. The Lewis acid is titanium tetrachloride, tin tetrachloride, boron trichloride, aluminum chloride or the like, and the organic compound is an organic compound having a functional group such as an alkoxy group, an acyloxy group or a halogen, for example, bis (2-methoxy-). 2-propyl) benzene, bis (2-
Examples include acetoxy-2-propyl) benzene and bis (2-chloro-2-propyl) benzene. Furthermore, if necessary, amides such as N, N-dimethylacetamide and esters such as ethyl acetate may be used as the third component together with the above Lewis acid and organic compound. Further, as an inert solvent for polymerization, hexane, cyclohexane, methylcyclohexane, methyl chloride, methylene chloride and the like can be used.

When a linear block copolymer is used as the A / B block copolymer, for example, (1) it has one functional group which produces a Lewis acid and a cationic polymerization active species as a polymerization initiator system. The compound is used to polymerize the vinyl aromatic monomer to form the polymer block (A), and then isobutylene is added to the reaction system to polymerize to form the polymer block (B). Polymer block by adding vinyl aromatic monomer and polymerizing (A)
(2) First, isobutylene is polymerized to form a polymer block (B) using a Lewis acid as a polymerization initiator system and a compound having two functional groups that generate a cationic polymerization active species. The method of adding a vinyl aromatic monomer to the reaction system to perform polymerization to form the polymer block (A) can be mentioned.

In the case of a branched block copolymer,
For example, a compound having three or more functional groups capable of generating a Lewis acid and a cationic polymerization active species is used as a polymerization initiator system, and isobutylene is first polymerized to form a polymer block.
After forming (B), a method in which a vinyl aromatic monomer is added and then polymerization is carried out to form the polymer block (A) can be adopted.

The number average molecular weight is 2,500 to 400,000.
0 polymer block (A) and number average molecular weight of 10,000
The above-mentioned A / having a number average molecular weight of 20,000 to 500,000 consisting of a polymer block (B) of ˜400,000.
The B block copolymer can be melt-spun, and the fiber of the present invention can be easily obtained according to a conventional melt-spinning method.

Prior to spinning, various additives may be optionally added to the A / B block copolymer. Examples of such additives include metal powder, silica, alumina, titanium oxide and the like. Inorganic particles such as metal oxides, calcium carbonate and barium sulfate, antioxidants, ultraviolet absorbers, heat-resistant agents, flame retardants, optical brighteners and colorants can be mentioned. In addition, other fiber-forming polymers may be used as long as they do not impair the properties such as high elasticity, high elastic recovery, vibration damping (vibration absorption), noise prevention, weather resistance, and heat aging resistance.
It may be blended with the / B block copolymer, and examples of such other polymer include polystyrene, polyolefin, polyamide, polyester, and hydrogenated styrene-diene block copolymer.

Further, the fiber comprising the A / B block copolymer of the present invention is the A / B block copolymer alone or only the A / B block copolymer composition prepared by blending the other fiber-forming polymer. Or an A / B block copolymer, or A / B
A composite fiber or a mixed spun fiber produced by composite spinning or mixed spinning with another fiber-forming polymer using a composition of a block copolymer and another polymer (hereinafter referred to as a composite fiber and a mixed spun fiber). Both are collectively called "composite fiber")
May be

In the case of the composite fiber, the proportion of the A / B block copolymer is 5% by weight or more based on the weight of all the polymers constituting the fiber, which means that the vibration damping performance (vibration absorption performance) is high. From the point of, it is preferable that the amount is 15% by weight or more. The composite form of the composite fiber is not particularly limited, and may be any of a core-sheath type, a sea-island type, a side-by-side type, a random composite type, and a mixture thereof. The polymer may be either a core component or a sheath component, and in the case of a sea-island type composite fiber, it may be either a sea component or an island component.

Among the conjugate fibers, a core-sheath type conjugate fiber having an A / B block copolymer as a core component and a fiber-forming polymer having a glass transition point of 45 ° C. or more as a sheath component is heated during melt spinning. It is preferable because it is less susceptible to deterioration and has excellent weather resistance. Examples of the sheath component in that case include polymers such as polystyrene, polyethylene terephthalate, polybutylene terephthalate, nylon 66, nylon 6, polyacrylonitrile, and the like, and particularly polyethylene terephthalate, nylon 6, nylon 66.
Is preferred. In a core-sheath type composite fiber having an A / B block copolymer as a core component, it is necessary to set the weight ratio of the core component and the sheath component to 9/1 to 1/9 so as to improve processability during spinning and drawing. From the viewpoint of damping performance of the obtained fiber, etc., 8/2 to 4/6 is more preferable. When a polyolefin such as polypropylene is mixed with the core component composed of the A / B block copolymer, stickiness of the polymer chip used for spinning can be prevented, and the core component composed of the A / B block copolymer is mixed with polybutene. 10 to 50% by weight
If it is blended to some extent, the fluidity during spinning can be improved.

In either case of the single fiber or the composite fiber, the cross-sectional shape of the fiber produced by using the A / B block copolymer is not particularly limited, and in addition to the usual round cross section, for example, a flat cross section, Any cross-sectional shape such as a polygonal cross-section, a multi-lobed cross-section, a hollow cross-section, a T-shaped cross-section, a V-shaped cross-section, or an array-type cross-section can be used. The thickness of the fiber is not particularly limited and may be appropriately selected depending on the application, etc., but is usually 1 to 5
A single fiber fineness of about 0 denier is preferable from the viewpoints of spinnability, handleability, knitting and weaving properties and the like.

The method for producing the fibers of the A / B block copolymer of the present invention or the composite fibers of the A / B block copolymer and another fiber-forming polymer is not particularly limited, and a conventionally known melt spinning apparatus is used. It can be produced by melt spinning using an apparatus similar to. For example, it can be manufactured by using a melt spinning apparatus of a type in which a gas pump is connected to a screw extruder. By selecting various spinning conditions such as spinning temperature, spinning extrusion pressure, extrusion speed, spinning hole diameter, and winding speed, it is possible to produce a fiber or yarn having a desired single fiber fineness and number of filaments. 180 ~ 300 ℃, spinning draft 5 ~ 200
If the winding speed is 20 to 1500 m / min, the target fiber can be smoothly produced. In order to prevent sticking between fibers after being wound up, apply an aqueous solution of a surfactant, an aqueous solution in which finely divided talc or calcium carbonate is dispersed, etc. to the spun yarn before winding. Is preferred. The wound fiber may or may not be drawn as in the case of normal thermoplastic synthetic fibers, and steps such as heat treatment may also be omitted, thus the spinning process is extremely simple. Therefore, the fiber of the present invention can be obtained economically.

The fibers made of the A / B block copolymer or the composite fibers made of the A / B block copolymer and another fiber-forming polymer may be in any form such as monofilament, multifilament and staple. Alternatively, it may be mixed or spun with other natural fibers or synthetic fibers to form a yarn, or may be used alone or in combination with other natural fibers or synthetic fibers to form a fabric such as a non-woven fabric or a knitted fabric, Therefore, the present invention also includes those yarns and cloths.

When a cloth is produced from fibers or composite fibers composed of an A / B block copolymer, it can be produced according to a conventionally known method for producing a cloth from thermoplastic polymer fibers. There is no particular limitation. In the case of a non-woven fabric, for example, the A / B block copolymer is melt-spun with other fiber-forming polymer as required, and the resulting fiber stream is formed by high-speed gas, and then collected in a sheet form. A non-woven fabric can be produced by a so-called melt blown direct molding method, and the melt blown method is disclosed in JP-A-49-10258, JP-A-49-48921, and JP-A-50-12157.
It can be produced according to the method described in JP-A No. 0-52.

The fibers, yarns and cloths of the present invention are excellent in stretchability, elastic recovery, vibration damping performance (vibration absorption), noise prevention, weather resistance, heat aging resistance, etc.
Flooring materials, interior materials for houses such as carpet bottoming materials, bandages,
It can be used in an extremely large number of applications as a base fabric for poultice, sports clothing, stockings, socks, foundation (underwear), and cotton stuffing for cushioning materials replacing conventional urethane foam. Especially when used as interior materials for homes such as wall materials, floor materials, and carpet bottom materials,
Due to its excellent vibration damping performance, it can absorb vibrations and sounds when walking, touching or bumping, keeping the room quiet. Further, when the nonwoven fabric of the present invention is used as a medical material such as a patch base fabric or bandage, due to its excellent stretchability, elastic recovery properties, etc., it moves following the movement of the affected part and from the affected part. It does not come off or come off.

[0030]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, number average molecular weight, mechanical loss coefficient (tan δ), breaking strength (strength), breaking elongation, 100% elongation recovery rate, 30%
The stress during stretching and the weather resistance (discoloration / fading) were measured or evaluated as follows.

Number average molecular weight : measured by GPC method. Mechanical loss coefficient (tan δ) : Using the non-woven mat (length 20 mm × width 3 mm × thickness 2 mm) obtained in each example, using Rhovibron (manufactured by Oriental Co., Ltd.),
Measure the temperature-dispersed viscoelastic spectrum and measure tan δ
I asked. This tan δ is a measure of the heat conversion rate of energy, and the larger this value, the greater the vibration damping performance (vibration absorption capacity).

Breaking strength and breaking elongation : JIS L 10
According to 96, it measured using the tensile tester (Shimadzu Corporation autograph). 100% elongation recovery rate : 1 according to JIS L 1096
It was released after 00% elongation and the residual strain was measured. Stress at 30% elongation : Measured using a tensile tester (Autograph manufactured by Shimadzu Corporation) according to JIS L 1096.

Weather resistance (discoloration / fading) : JIS L 1096
According to the above, an outdoor exposure test was carried out for 1 month to measure the discoloration and fading of the sample.

<Production Example 1> [Production of A / B block copolymer (1)] 800 ml of methylene chloride and 120 of methylcyclohexane as a solvent in a reactor equipped with a stirrer.
0 ml, titanium tetrachloride (Lewis acid) as polymerization initiator system
4.3 g and 1,3-bis (2-methoxy-2-propyl) benzene 0.33 g were charged, 210 g of isobutylene was charged at -65 ° C. and polymerized for 4 hours, then 0.13 g of dimethylacedamide and 90 g of styrene. And further polymerized for 4 hours to obtain an A / B block copolymer (1) comprising a styrene polymer block [polymer block (A)] and an isobutylene polymer block [polymer block (B)].
Was synthesized. The number average molecular weight of the polymer block (A) in the obtained A / B block copolymer (1) was 60,000.
0, the number average molecular weight of the polymer block (B) is 140,000
And the number average molecular weight of the A / B block copolymer (1) was 200,000. When examined by NMR, the styrene content in the A / B block copolymer (1) was 30% by weight.

<Production Example 2> [Production of A / B block copolymer (2)] The amount of isobutylene initially charged was 150.
g, and styrene polymer block [polymer block (A)] and isobutylene polymer block [polymer block (B)] in the same manner as in Production Example 1 except that the amount of styrene charged next was 38 g. Was synthesized to synthesize an A / B block copolymer (2). The number average molecular weight of the polymer block (A) in the obtained A / B block copolymer (2) was 2
5,000, the number average molecular weight of the polymer block (B) is 10
And the number average molecular weight of the A / B block copolymer (2) was 125,000. When examined by NMR, the styrene content in the A / B block copolymer (2) was 20% by weight.

<Production Example 3> [Production of A / B block copolymer (3)] The amount of isobutylene initially charged was 90.
g, styrene polymer block [polymer block (A)] and isobutylene polymer block [polymer block (B)] in the same manner as in Production Example 1 except that the amount of styrene charged next was 45 g. Was synthesized to synthesize an A / B block copolymer (3). The number average molecular weight of the polymer block (A) in the obtained A / B block copolymer (3) was 3
000, the number average molecular weight of the polymer block (B) is 6
And the number average molecular weight of the A / B block copolymer (3) was 90,000. When examined by NMR, the styrene content in the A / B block copolymer (3) was 35% by weight.

<Production Example 4> [Production of hydrogenated St / Ip block copolymer (1)] 3000 g of methylcyclohexane as a solvent and n-butyllithium as a polymerization catalyst in a pressure resistant reactor substituted with dry nitrogen. 7g, styrene 6
After charging 0g and polymerizing for 1 hour, 300g isoprene
Was charged and polymerized for 2 hours, and then 60 g of styrene was charged and polymerized for 1 hour to produce a triblock copolymer composed of a styrene polymer block-isoprene polymer block-styrene polymer block. In the obtained triblock copolymer, the number average molecular weight of the styrene polymer block copolymer was 65,000, the number average molecular weight of the isoprene polymer block copolymer was 145,000, and the number average molecular weight of the entire triblock copolymer was The molecular weight was 210,000. When examined by NMR, the styrene content in the triblock copolymer was 30% by weight. A cyclohexane solution of the obtained triblock copolymer was prepared, and a palladium catalyst (hydrogenation catalyst) was added thereto, and the hydrogen pressure was 20 k.
Hydrogenation reaction is carried out under the condition of g / cm ² to give a hydrogenated block copolymer [hydrogenated St / Ip block copolymer (1)].
(Hydrogenation rate of 97%) was obtained.

The contents of the block copolymers obtained in Production Examples 1 to 4 are summarized in Table 1 below.

[0039]

[Table 1]

Example 1 A / B obtained in Production Example 1
The block copolymer (1) was spun at a spinning temperature of 20 using an ordinary spinning machine in which a gear pump was combined with a screw type extruder.
Spin at 0 ° C. and spinning speed of 500 m / min to obtain a single fiber fineness of 4
A 0 denier filament was produced. The breaking elongation of this fiber was 550%, the breaking strength was 0.8 g / d, and the 100% elongation recovery rate was 95% or more. The fibers were cut to produce staples having a fiber length of 64 mm. These staples were well mixed, carded, and laminated at random to form a web, and a mat heat-treated at 150 ° C. for 1 minute was produced. The thickness of the mat is 2 mm and the basis weight is about 1 k
It was g / cm ² . When the tan δ at 25 ° C. of the obtained mat was measured, it was as shown in Table 2 below.

<< Examples 2-3 >> A obtained in Production Example 2
Spinning was performed in the same manner as in Example 1 except that the A / B block copolymer (2) and the A / B block copolymer (3) obtained in Production Example 3 were used, respectively, to obtain a single fiber fineness of 40 denier. Filaments were produced. The breaking elongation, breaking strength and 100% elongation recovery rate of this fiber were as shown in Table 2 below. This was cut to produce staples having a fiber length of 64 mm, a web was formed in the same manner as in Example 1 and heat treated at 150 ° C. for 1 minute to prepare a mat. The thickness of the mat was 2 mm and the basis weight was about 1 kg / cm ² . About the obtained mat 25
The tan δ at ° C was measured and found to be as shown in Table 2 below.

Example 4 A / B obtained in Example 1
After 80 parts by weight of the staple of the block copolymer (1) fibers were mixed with 20 parts by weight of the polyester-based heat-fusible fiber staple having a single fiber fineness of 40 denier and a fiber length of 51 mm, the same thickness as in Example 1 was applied. 2 mm, unit weight approximately 1 kg
A mat of / cm ² was produced. The tan δ at 25 ° C. of the obtained mat was measured and the results are shown in Table 2 below.
It was as shown in.

Comparative Example 1 Hydrogenated S obtained in Production Example 4
When a fiber was produced by melt spinning using the t / Ip block copolymer (1) in the same manner as in Example 1, the breaking elongation, breaking strength and 100% elongation recovery rate of the obtained fiber were as follows. It was as shown in Table 2. This was cut to produce staples having a fiber length of 64 mm, and in the same manner as in Example 1, a mat having a thickness of 2 mm and a basis weight of about 1 kg / cm ² was produced. About the obtained mat, tan δ at 25 ° C
Was measured and found to be as shown in Table 2 below.

Comparative Example 2 Hydrogenated S obtained in Production Example 4
When a fiber was produced by melt spinning using the t / Ip block copolymer (1) in the same manner as in Example 1, the breaking elongation, breaking strength and 100% elongation recovery rate of the obtained fiber were as follows. It was as shown in Table 2. This is cut to produce staples having a fiber length of 64 mm.
After mixing 20 parts by weight of polyester-based heat-fusible fiber staple having a monofilament fineness of 40 denier and a fiber length of 51 mm to the parts by weight, a mat having a thickness of 2 mm and a basis weight of about 1 kg / cm ² was prepared in the same manner as in Example 1. Manufactured. When the tan δ at 25 ° C. of the obtained mat was measured, it was as shown in Table 2 below.

[0045]

[Table 2]

From the results shown in Table 2 above, the mats obtained by using the fibers of Examples 1 to 4 made of the A / B block copolymer were the same as Comparative Example 1 made of the hydrogenated styrene / isoprene block copolymer. Compared to the mat obtained from the fibers of ~ 2, tan δ is remarkably large and vibration damping performance is excellent.
It can be seen that it is effective as a soundproof material.

Example 5 A / B obtained in Production Example 1
The block copolymer (1) is used as a core component, and the intrinsic viscosity is 0.6.
Polyethylene terephthalate No. 4 as a sheath component was supplied to a core-sheath type composite spinning device at a weight ratio of core component: sheath component = 85: 15, spinning temperature 290 ° C., winding speed 100 m /
After performing melt-composite spinning according to the usual method in minutes, it is stretched and then is a concentric core-sheath conjugate fiber (single fiber fineness of 8 denier).
Got Cutting elongation, breaking strength and 100% of this fiber
The elongation recovery rate was as shown in Table 3 below. After this was cut to produce a staple having a fiber length of 64 mm, 80 parts by weight of the staple were mixed with 20 parts by weight of a polyester-based heat-fusible fiber staple having a single fiber fineness of 3 denier and a fiber length of 51 mm, and then an example was obtained. Thickness 2 as in 1
mm, and a mat having a basis weight of about 0.5 kg / cm ² was produced. When the tan δ at 25 ° C. of the obtained mat was measured, it was as shown in Table 3 below. The weather resistance (discoloration and fading) of the obtained mat is shown in Table 3 below.
It was as follows.

Example 6 A / B obtained in Production Example 2
The block copolymer (2) is used as a core component, and the intrinsic viscosity is 0.6.
Polyethylene terephthalate of 4 was used as a sheath component at a weight ratio of core component: sheath component = 70: 30 to a core-sheath composite spinning apparatus, and spinning and drawing were performed in the same manner as in Example 5 to form a concentric core sheath. A type composite fiber (single fiber fineness of 8 denier) was obtained. The breaking elongation, breaking strength and 100% elongation recovery rate of this fiber were as shown in Table 3 below. After this was cut to produce a staple having a fiber length of 64 mm, 80 parts by weight of this staple were mixed with 20 parts by weight of the same polyester-based heat-fusible fiber staple used in Example 5, and then Example 5 Similarly to the above, the thickness is 2 mm and the basis weight is about 0.
A 5 kg / cm ² mat was produced. The tan δ and weather resistance (discoloration) of the obtained mat at 25 ° C. are shown in Table 3 below.

Example 7 A / B obtained in Production Example 1
A 1/1 (weight ratio) mixture of the block copolymer (1) and the A / B block copolymer (3) obtained in Production Example 3 was used as a core component, and polyethylene terephthalate having an intrinsic viscosity of 0.64 was used as a sheath component. As a core component: sheath component = 50: 50 in a weight ratio, the core-sheath type composite spinning device is supplied to the core-sheath type composite spinning device and spun and drawn in the same manner as in Example 5 to form a concentric core-sheath type composite fiber (single fiber fineness 8 denier) was obtained. The breaking elongation, breaking strength and 100% elongation recovery rate of this fiber were as shown in Table 3 below. After this was cut to produce a staple having a fiber length of 64 mm, 80 parts by weight of this staple were mixed with 20 parts by weight of the same polyester-based heat-fusible fiber staple used in Example 5, and then Example 5 A mat having a thickness of 2 mm and a basis weight of about 0.5 kg / cm ² was manufactured in the same manner as in. The tan δ and weather resistance (discoloration) of the obtained mat at 25 ° C. are shown in Table 3 below.

Comparative Example 3 Hydrogenated S obtained in Production Example 4
The t / Ip block copolymer (1) was used as a core component, and polyethylene terephthalate having an intrinsic viscosity of 0.64 was used as a sheath component, and the weight ratio of the core component: the sheath component = 85: 15 was supplied to the core-sheath composite spinning device. Then, spinning and drawing were carried out in the same manner as in Example 5 to obtain a concentric core-sheath type composite fiber (single fiber fineness 8 denier). The breaking elongation, breaking strength and 10 of this fiber
The 0% elongation recovery rate was as shown in Table 3 below. This was cut to produce a staple having a fiber length of 64 mm, and then 80 parts by weight of this staple were mixed with 20 parts by weight of the same polyester-based heat-fusible fiber staple used in Example 5 to obtain Example 5. A mat was manufactured in the same manner.
The tan δ and weather resistance (discoloration) of the obtained mat at 25 ° C. are shown in Table 3 below.

<< Comparative Example 4 >> Hydrogenated S obtained in Production Example 4
The t / Ip block copolymer (1) was used as a core component, and polyethylene terephthalate having an intrinsic viscosity of 0.64 was used as a sheath component, and the mixture was supplied to a core-sheath composite spinning device at a weight ratio of core component: sheath component = 50: 50. Then, spinning and drawing were carried out in the same manner as in Example 5 to obtain a concentric core-sheath type composite fiber (single fiber fineness 8 denier). The breaking elongation, breaking strength and 10 of this fiber
The 0% elongation recovery rate was as shown in Table 3 below. This was cut to produce a staple having a fiber length of 64 mm, and then 80 parts by weight of this staple were mixed with 20 parts by weight of the same polyester-based heat-fusible fiber staple used in Example 5 to obtain Example 5. A mat was manufactured in the same manner.
The tan δ and weather resistance (discoloration) of the obtained mat at 25 ° C. are shown in Table 3 below.

[0052]

[Table 3]

From the results shown in Table 3 above, the mats obtained from the fibers of Examples 5 to 7 made of the A / B block copolymer were compared to Comparative Examples 3 to 4 made of the hydrogenated styrene / isoprene block copolymer. Ta compared to mats obtained from fibers
It can be seen that nδ is remarkably large and excellent in vibration damping performance, is effective as a vibration absorbing material and a soundproofing material, and has good weather resistance and no discoloration or fading.

Example 8 A / B obtained in Production Example 1
After melting the block copolymer (1) with a screw type extruder, it is fed into a die of 270 ° C., a melt blown spinning device having orifices of 0.3 mmφ arranged at a pitch of 1 mm and having jet slits of heated gas on both sides, The block copolymer is discharged at a rate of 0.2 g per hole,
Air heated to 265 ° C was added to the weight of the block copolymer of 4
It was thinned by injecting 0 times the amount. This was collected on a wire mesh belt placed 15 cm below the nozzle and wound by a winder downstream to manufacture a nonwoven fabric. As a result, a nonwoven fabric having a basis weight, a breaking strength, a 100% elongation recovery rate, a 30% elongation stress and a weather resistance shown in Table 4 below was obtained.

Example 9 A / B obtained in Production Example 1
A non-woven fabric was produced in the same manner as in Example 8 using the block copolymer (1) under the conditions shown in Table 4 below. The fabric weight, breaking strength, 100% elongation recovery rate, and 30 shown in Table 4 were obtained.
A non-woven fabric having a% elongation stress and weather resistance was obtained.

Example 10 A / A obtained in Production Example 2
A non-woven fabric was produced in the same manner as in Example 8 using the B block copolymer (2) under the conditions shown in Table 4 below.
Unit weight shown in Table 4, breaking strength, 100% elongation recovery rate, 3
A nonwoven having 0% elongation stress and weather resistance was obtained.

Example 11 A / A obtained in Production Example 3
A non-woven fabric was produced in the same manner as in Example 8 using the B block copolymer (1) under the conditions shown in Table 4 below.
Unit weight shown in Table 4, breaking strength, 100% elongation recovery rate, 3
A nonwoven having 0% elongation stress and weather resistance was obtained.

Comparative Example 5 Hydrogenated S obtained in Production Example 4
When a non-woven fabric was produced using the t / Ip block copolymer (2) under the conditions shown in Table 4 below in the same manner as in Example 8, the basis weight, breaking strength, 100% elongation recovery rate shown in Table 4, A non-woven fabric having a stress at 30% elongation and weather resistance was obtained.

[0059]

[Table 4]

From the results shown in Table 4 above, the nonwoven fabrics of Examples 8 to 11 of the present invention comprising A / B block copolymer fibers were
It can be seen that it is excellent in properties such as breaking strength and 100% elongation recovery rate, and is also excellent in weather resistance (discoloration resistance) as compared with the nonwoven fabric of Comparative Example 5 made of hydrogenated styrene / isoprene block copolymer fiber. .

[0061]

The fiber, yarn and cloth of the present invention comprising the A / B block copolymer have excellent stretchability, elastic recovery and
It has properties such as vibration damping performance (vibration absorption capacity), noise prevention, weather resistance, and heat aging resistance, and can be effectively used in a wide range of applications. More specifically, the fiber, yarn and cloth of the present invention have high elasticity and excellent stretchability, so that they have vibration damping performance (vibration absorption) and are required to have noise prevention ability and vibration absorption ability. It can be effectively used for an extremely wide range of applications such as wall materials, flooring materials, interior materials such as carpet bottom materials, cushioning materials, sports clothing, stockings and socks, foundations, base materials for poultices and bandages. Since it does not have an unsaturated double bond in the molecule of the coalescence,
It has excellent weather resistance, heat resistance, and heat aging resistance, is resistant to discoloration and yellowing, and can maintain a good appearance and color tone for a long period of time. Moreover, the fiber made of the A / B block copolymer of the present invention does not require vulcanization, and in some cases, stretching treatment or heat treatment, and can be manufactured by an extremely simple process.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D04H 1/42 J 7199-3B 1/54 H 7199-3B (72) Inventor Mizuho Maeda Kashima, Ibaraki Prefecture 36, Towada, Kamisu-cho, Kuraray Co., Ltd.

Claims (5)

[Claims] 1. A polymer block (A) having a number average molecular weight of 2,500 to 400,000 made of a vinyl aromatic monomer and a number average molecular weight of 10, made of isobutylene.
A fiber produced by using a block copolymer having a number average molecular weight of 20,000 to 500,000, which is composed of a polymer block (B) of 000 to 400,000. 2. The fiber of claim 1 made from a block copolymer homopolymer or a composition of a block copolymer and another thermoplastic polymer. 3. The fiber according to claim 1, which is a mixed spun fiber or a composite fiber produced by mixed spinning or composite spinning using a block copolymer and another thermoplastic polymer. 4. A yarn produced using the fiber according to any one of claims 1 to 3. 5. A fabric manufactured using the fiber according to any one of claims 1 to 3 or the yarn according to claim 4.