KR20180116681A - Thermal bonding fiber and thermal bonding fiber composite - Google Patents

Abstract

The present invention relates a technique for excellent mechanical properties such as strength, elasticity, elongation and the like, can lower a thermal bonding temperature to increase process efficiency while preventing fiber damage, and can improve the bonding strength and ensure excellent durability, and specifically, to a thermal bonding fiber and to a thermal bonding fiber composite, wherein the thermal bonding fiber comprises: a core comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 55 to 90D; and a sheath including a thermoplastic polyester elastomer resin formed on the core and having a Shore D hardness of 20 to 50D and a copolyester resin having a melting temperature of 80 to 150°C.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermally adhesive fiber,

The present invention relates to a thermally adhesive fiber and a thermally adhesive fibrous composite. More particularly, the present invention relates to a thermosetting resin composition which is excellent in mechanical properties such as strength, elasticity, and elongation, can lower the heat bonding temperature to improve the process efficiency while preventing fiber damage, To an adhesive fiber composite.

Generally, a polyester copolymer elastomer prepared by reacting an aromatic dicarboxylic acid together with a polyol mixture such as an alkylene glycol and a polyalkylene glycol oxide has excellent physical and chemical properties, flexibility and strength, and electrical insulation characteristics It is widely applied to various molded products and wire covering materials.

In recent years, studies have been actively conducted on thermo-adhesive conjugated fibers in which mono filaments are produced by incorporating a polyester-copolymerized elastomer as a main component of cores and sheath, respectively, and then thermally adhering through a solidification process by heat- have.

However, since the polyester copolymer elastomer itself has a high melting temperature exceeding 150 캜, heat treatment at a temperature higher than the melting temperature of the polyester copolymer elastomer is indispensably required in order to proceed heat bonding between the polyester copolymer elastomers There was a limit.

Accordingly, it is required to develop new heat-bonding fibers capable of lowering the heat bonding temperature in the production of heat-bonding fibers, while maintaining excellent mechanical properties of the conventional polyester-copolymerized elastomer at an equivalent level or higher.

An object of the present invention is to provide a thermally adhesive fiber capable of improving mechanical properties such as strength, elasticity and elongation, and lowering a heat bonding temperature to thereby prevent fiber damage while improving process efficiency.

Further, the present invention is to provide a thermally adhesive fiber composite comprising the thermally adhesive fiber.

In the present specification, a core comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 55D to 90D; And a thermosetting polyester fiber formed on the core and comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 20 D to 50 D and a sheath containing a copolyester resin having a melting temperature of 80 to 150 캜.

Also disclosed herein is a thermally adhesive fibrous composite comprising thermally adhesive fibers.

The heat-adhesive fiber and the heat-adhesive fiber composite according to a specific embodiment of the present invention will be described in detail below.

Whenever a component is referred to as "comprising ", it is understood that it may include other components as well, without departing from the other components unless specifically stated otherwise.

In the present specification, "*" means a point of attachment, specifically, a point of attachment of a repeating unit represented by the formula (1) or (2) to another repeating unit.

In the present specification, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector, and an analyzing column can be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 DEG C, a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

In this specification, a core and a sheath can refer to a cis-shaped structure that externally surrounds an inner core.

In the present specification, an example of a method of measuring the Shore D hardness is not limited, but may be measured according to the method specified in ASTM D 2240.

In the present specification, examples of a method of measuring the melting temperature, the glass transition temperature and the crystallization temperature are not limited, but the temperature is maintained at 300 DEG C for 5 minutes using a DSC measuring machine (manufacturer: Mettler Toledo, DSC1, star system) And then slowly cooled to room temperature and then resampled at a temperature raising rate of 10 DEG C / min to measure.

In the present specification, examples of the method of measuring the intrinsic viscosity are not limited. For example, the measurement object is dissolved at a concentration of 0.12% in 150 占 폚 o-chlorophenol (OCP) A method of measuring using a viscometer can be used.

As used herein, the term " residue " refers to a certain moiety or unit derived from the specific compound that is included in the result of the chemical reaction when the particular compound participates in the chemical reaction. For example, each of the 'residue' of the dicarboxylic acid component or the 'residue' of the diol component may be derived from a dicarboxylic acid component or a diol component in a polyester formed by an esterification reaction or a polycondensation reaction It means the part derived.

According to one embodiment of the invention, a core comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 55D to 90D; And thermosetting polyester fibers formed on the core and comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 20D to 50D and a sheath containing a copolyester resin having a melting temperature of 80 DEG C to 150 DEG C .

The inventors of the present invention have found that when thermally adhesive fibers obtained by mixing a thermoplastic polyester elastomer resin having a cis-Shore D hardness of 20 D to 50 D and a copolyester resin having a melting temperature of 80 to 150 캜, It was confirmed that the thermal bonding between the core and the sheath proceeds at a lower temperature by lowering the melting temperature of the sheath, and the invention was completed.

In particular, the copolyester resin having a melting temperature of 80 to 150 ° C can improve the initial adhesion to the core while lowering the melting temperature of the sheath through a low temperature melting temperature, So that the durability of the thermally adhesive fiber can be ensured even when there is a long-term storage.

The copolyester resin having a melting temperature of 80 ° C to 150 ° C is excellent in compatibility with the thermoplastic polyester elastomer resin so that the mechanical properties of the thermoplastic polyester elastomer at the time of mixing are equal to or more than that of the thermoplastic polyester elastomer, It is possible to realize the durability enhancement effect by the same.

Hereinafter, the constituent elements of the thermally adhesive fiber of the embodiment will be described in detail.

core

The core may comprise a thermoplastic polyester elastomer resin having a Shore D hardness of 55D to 90D. That is, the thermoplastic polyester elastomer resin contained in the core can have a higher hardness than that of the thermoplastic polyester elastomer resin contained in the sheath, so that the thermally adhesive fiber finally produced can have high strength.

The thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D may contain a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), respectively.

[Chemical Formula 1]

In Formula 1, m is 2 to 6, X is an integer of 1 or more,

(2)

In Formula 2, n is 2 to 6, p is 10 to 30, and Y is an integer of 1 or more.

Specifically, the repeating unit represented by Formula 1 is an ester repeating unit obtained through an esterification reaction between an aromatic dicarboxylic acid or a derivative thereof and an aliphatic diol, and the repeating unit represented by Formula 2 is an aromatic dicarboxylic acid or a derivative thereof and a polyether Corresponds to an ester repeating unit obtained through an esterification reaction between diols.

Examples of the aromatic dicarboxylic acid or its derivative include dimethyl terephthalate, dimethyl isophthalate, terephthalic acid, isophthalic acid, and 2,6-naphtha dicarboxylic acid. Examples of the aliphatic diol include butane diol and hexane diol . Examples of the polyether diol include polyalkylene ether glycols having a weight average molecular weight of 500 g / mol to 2000 g / mol.

Preferably, in Formula 1, m is 4 and X is an integer of 1 or more. In Formula 2, n is 4, p is 10 to 30, and Y is an integer of 1 or more.

More specifically, the thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D has a repeating unit represented by the above formula (2) in an amount of less than 12 mol%, or 0.1 mol% or more and less than 12 mol% Mol% to less than 12 mol%.

That is, the amount of the repeating unit represented by the formula (2) is less than 12 moles, or less than 0.1 moles and less than 12 moles, or less than 1 moles and less than 12 moles, based on 100 moles of the thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D ≪ / RTI > As described above, the thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D can satisfy the high hardness because the soft segment ratio derived from the polyether diol is relatively low as in the case of the repeating unit represented by the formula (2).

Cis

The sheath may comprise a thermoplastic polyester elastomer resin having a Shore D hardness of 20 D to 50 D and a copolyester resin having a melting temperature of 80 to 150 캜.

First, the sheath may include a thermoplastic polyester elastomer resin having a Shore D hardness of 20D to 50D. That is, the thermoplastic polyester elastomer resin contained in the sheath can have a lower hardness than that of the thermoplastic polyester elastomer resin contained in the core, and can have a low melting temperature as well, The efficiency of the system can be increased.

The thermoplastic polyester elastomer resin having Shore D hardness of 20D to 50D may contain a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), respectively.

[Chemical Formula 1]

In Formula 1, m is 2 to 6, X is an integer of 1 or more,

(2)

In Formula 2, n is 2 to 6, p is 10 to 30, and Y is an integer of 1 or more.

The description of Formulas (1) and (2) above includes the above description of the core.

The thermoplastic polyester elastomer resin having Shore D hardness of 20D to 50D may contain 12 mol% or more, or 12 mol% to 30 mol% of the repeating unit represented by the above formula (2) with respect to the total resin.

That is, the repeating unit represented by the formula (2) may be contained in an amount of 12 mol or more, or 12 mol to 30 mol based on 100 mol of the thermoplastic polyester elastomer resin having the Shore D hardness of 20D to 50D. As described above, the thermoplastic polyester elastomer having a Shore D hardness of 20D to 50D has a relatively high soft segment ratio derived from a polyether diol as in the case of the repeating unit represented by the formula (2), so that it can satisfy a low hardness and a low melting temperature .

Further, the sheath may contain a copolyester resin having a melting temperature of 80 ° C to 150 ° C. If the thermosetting fiber obtained by mixing the thermosetting polyester elastomer resin having the Shore D hardness of 20D to 50D with the copolyester resin having the melting temperature of 80 to 150 DEG C is used in the sheath, It is possible to improve the initial adhesion strength with the core as well as to improve the durability of the thermally adhesive fiber due to less change in the adhesive strength even during long-term storage.

Specifically, the melting temperature of the sheath may be 130 ° C to 150 ° C. Considering that the melting temperature of the thermoplastic polyester elastomer resin having the Shore D hardness of 20D to 50D is measured at 155 占 폚 to 200 占 폚, only the thermoplastic polyester elastomer having the Shore D hardness of 20D to 50D exists in the sheath , The melting temperature of the sheath is necessarily higher than 155 ° C. However, by blending a thermoplastic polyester elastomer resin having a Shore D hardness of 20 D to 50 D with a copolyester resin having a melting point and a melting point of 80 to 150 캜, the melting temperature of the sheath is lowered to 150 캜 or lower .

Wherein the copolyester resin having a melting temperature of from 80 DEG C to 150 DEG C is a residue of a diol component comprising an alicyclic diol or an aliphatic diol; And residues of dicarboxylic acid components including aliphatic dicarboxylic acids or derivatives thereof, alicyclic dicarboxylic acids or derivatives thereof, aromatic dicarboxylic acids or derivatives thereof.

Based on the whole copolyester resin, 5 to 40% by weight of the alicyclic diol, 10 to 45% by weight of an aliphatic diol, 5 to 40% by weight of an alicyclic dicarboxylic acid or a derivative thereof, 10% by weight to 45% by weight of a carboxylic acid or a derivative thereof.

When the content of the alicyclic dicarboxylic acid or its derivative is less than 5% by weight based on the total copolyester resin, sufficient flexibility can not be secured while replacing the aliphatic acid. Conversely, when the content of the alicyclic dicarboxylic acid or its derivative exceeds 40% There is a possibility that the crystallinity is deteriorated and the characteristics of the inherently crystalline hot-melt resin can not be exhibited.

If the content of the aromatic dicarboxylic acid or its derivative is less than 10% by weight based on the total amount of the copolyester resin, there is a problem of deteriorating the crystallinity. If the content exceeds 45% by weight, sufficient flexibility can not be secured .

If the content of the alicyclic diol is less than 5% by weight based on the total amount of the copolyester resin, the hydrolysis resistance may decrease. If the content of the alicyclic diol exceeds 40% by weight, flexibility can not be secured.

If the amount of the aliphatic diol is less than 10% by weight based on the total amount of the copolyester resin, there is a problem that flexibility can not be ensured. If the amount exceeds 45% by weight, the hydrolysis resistance may decrease.

Also, it is preferable that 30% by weight to 70% by weight of the aliphatic diol, 5% by weight to 40% by weight of the aliphatic dicarboxylic acid or its derivative and 20% by weight of the aromatic dicarboxylic acid or its derivative, By weight to 60% by weight.

In the present specification, a derivative means a compound in which the structure and properties of a host such as introduction of a functional group, oxidation, reduction, substitution of an atom, etc., are changed not to significantly change with the compound as a parent, and specifically, the aliphatic dicarboxylic acid, Examples of derivatives of dicarboxylic acid compounds such as alicyclic dicarboxylic acids or aromatic dicarboxylic acids include dicarboxylic acid ester compounds.

Examples of the aliphatic dicarboxylic acid or derivatives thereof include straight chain or branched chain alkane dicarboxylic acids having 2 to 20 carbon atoms; And derivatives thereof. Specific examples of the straight-chain or branched-chain alkane dicarboxylic acid having 2 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, and pimelic acid. Of these, adipic acid Is preferably used.

Examples of the alicyclic dicarboxylic acid or derivatives thereof include cycloalkane dicarboxylic acids having 5 to 30 carbon atoms; Or a derivative thereof, and as the derivative of the cycloalkane dicarboxylic acid having 5 to 30 carbon atoms, a dialkyl cycloalkane dicarboxylic acid ester having 5 to 30 carbon atoms can be used.

Specific examples of the cycloalkane dicarboxylic acid having 5 to 30 carbon atoms include 1,4-cyclohexane dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, . Specific examples of the dialkyl cycloalkane dicarboxylic acid ester having 5 to 30 carbon atoms include dimethyl-1,4-cyclohexanedicarboxylate. For economical and flexible reasons, dimethyl-1 , 4-cyclohexanedicarboxylate is most preferably used.

Examples of the aromatic dicarboxylic acid or its derivatives include arene dicarboxylic acid having 8 to 30 carbon atoms; Or a derivative thereof, and as the derivative of the diallyl dicarboxylic acid having 8 to 30 carbon atoms, a dialkylarene dicarboxylic acid ester having 8 to 30 carbon atoms can be used.

Specific examples of the above-mentioned arene dicarboxylic acid having 8 to 30 carbon atoms include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and the like, and the dialkylenedicarboxylic acid ester having 8 to 30 carbon atoms Specific examples thereof include dimethyl terephthalate and dimethyl isophthalate, and it is preferable to use dimethyl terephthalate or dimethyl isophthalate in view of suppressing reaction rate and side reaction.

Examples of the alicyclic diols include cycloalkane diols having 3 to 20 carbon atoms. Specific examples of the cycloalkane diol having 3 to 20 carbon atoms include 1,4-cyclohexane dimethanol, tricyclodecane dimethanol May be used. In view of flexibility, 1,4-cyclohexanedimethanol is preferable.

Examples of the aliphatic diols include linear or branched alkane diols having 1 to 20 carbon atoms. Specific examples of the straight or branched chain alkene diols having 1 to 20 carbon atoms include butane diol and hexane diol. Double butanediol is most preferred.

The copolyester resin having a melting temperature of 80 ° C to 150 ° C may have an intrinsic viscosity of 0.2 dl / g to 0.9 dl / g.

The copolyester resin having a melting point of 80 to 150 캜 has a glass transition temperature (measured by DSC) of -30 캜 to 10 캜 and a crystallization temperature (measured by DSC) of 50 캜 to 80 캜 .

The method of producing the copolyester resin having the melting temperature of 80 to 150 DEG C is not limited to a great degree. For example, the following method can be used. An alicyclic dicarboxylic acid or a derivative thereof, an aromatic dicarboxylic acid or a derivative thereof, an alicyclic diol, and an aliphatic diol are charged as a reactant into a reactor equipped with a column and a condenser, or an aliphatic diol, aliphatic dicarboxylic acid Or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof and then gradually raising the temperature of the reactor. When the temperature of the reactor reaches 130 to 150 ° C, the reaction catalyst is introduced, and then the temperature of the reactor is adjusted to 200 to 270 ° C The temperature of the column is maintained at 100 ° C so that the reaction product which has been heated to raise the esterification reaction does not evaporate or sublimate, so that only reaction by-products such as water and methanol are allowed to escape.

When the esterification reaction is carried out for about 1 hour to 10 hours, the reaction is terminated and reaction by-products such as water and methanol no longer appear, and the reactant in the white slurry state becomes a pale yellow transparent oligomer. The oligomer obtained in the esterification reaction is heated to 220 to 300 DEG C and the vacuum is gradually reduced to 0.01 to 5 torr while taking care not to scatter the reactant. In this process, the reaction is allowed to proceed for 30 minutes to 10 hours while removing the diol component flowing out as reaction by-products.

On the other hand, the mixing ratio of the thermoplastic polyester elastomer resin having a Shore D hardness of 20 D to 50 D contained in the sheath and the copolyester resin having a melting temperature of 80 to 150 캜 is, for example, a Shore D hardness of 20 D to 50 D The content of the copolyester resin having a melting temperature of 80 to 150 占 폚 may be 10 to 50 parts by weight or 20 to 40 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer resin.

If the content of the copolyester resin having the melting temperature of 80 to 150 ° C is excessively decreased, it is difficult to sufficiently realize the effect of decreasing the melting temperature and improving the durability by the copolyester resin, If the content of the copolyester resin at 150 ° C is excessively increased, the tensile properties and the elastic properties of the thermoplastic polyester elastomer resin may decrease, and the mechanical properties of the thermally adhesive fiber may be reduced.

Thermal adhesion  fiber

Wherein the thermally adhesive fiber has a core comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 55D to 90D; And a sheath formed on the core, the sheath including a thermoplastic polyester elastomer resin having a Shore D hardness of 20D to 50D and a copolyester resin having a melting temperature of 80 ° C to 150 ° C. The sheath is formed on the core, and can be bonded to the core to form a core-cis double structure fiber.

The thermally adhesive fibers may have an average cross-sectional diameter of 100 μm to 500 μm, and the length is not particularly limited. The cross-sectional diameter means the maximum diameter of the cross-sectional shape of the thermally adhesive fiber. At this time, the average cross-sectional diameter of the core may be 80 to 400 占 퐉, and the average cross-sectional diameter of the sheath may be 20 to 100 占 퐉. The average cross-sectional diameter of the sheath can be found by subtracting the average cross-sectional diameter of the core from the average cross-sectional diameter of the entire heat-bondable fibers.

On the other hand, the content of the thermoplastic polyester elastomer resin having Shore D hardness of 20D to 50D is preferably 1 part by weight to 50 parts by weight, or 10 parts by weight or less, based on 100 parts by weight of the thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D To 30 parts by weight. If the content of the thermoplastic polyester elastomer resin having the Shore D hardness of 20D to 50D is excessively increased relative to 100 parts by weight of the thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D, .

The thermally adhesive fibers can be used as a material for a chair, a running shoes, a curtain, or an automobile mat. More specifically, the present invention can be applied to a mesh material of a mesh chair, a sheath of a lightweight sneaker, and a curtain material.

The core or sheath of the thermally adhesive fiber may be added with various additives for improving the physical properties and the like as needed. The kind of the additive, the method of introduction and the time of injection are not particularly limited and various known contents can be applied without limitation. Specific examples of the additive include impact modifiers, antioxidants, compatibilizers, hydrolysis stabilizers, Stabilizers, color additives and fixing agents, flame retardants, or electroconductive materials for the loss of static electricity.

Examples of the method for producing the heat-bondable fiber are not limited to a wide range. For example, a variety of known composite radiation methods can be used without limitation.

On the other hand, according to another embodiment of the invention, a thermally adhesive fibrous composite comprising the thermally adhesive fiber of one embodiment of the present invention can be provided.

The content of the thermally adhesive fiber includes all of the above-mentioned contents in one embodiment.

The thermally adhesive fibrous composite may comprise a thermally adhesive fibrous cross-section of a porous mesh structure. The thermally adhesive fiber crossing may form a porous mesh structure through the intersection of a plurality of thermally adhesive fibers. Specifically, the thermally adhesive fiber crossing may have a mesh diameter of 0.5 mm to 5 mm.

More specifically, in the thermally adhesive fiber crossing, the thermally adhesive fibers may be fused at each crossing point. The intersection point means a point where two or more thermally adhesive fibers intersect with each other, and the thermally adhesive fibers can be bonded to each other while the thermally adhesive fibers are fused at the intersections.

More specifically, it can be fused at a depth of 20 占 퐉 or less from the outermost surface of the thermally adhesive fiber. That is, at the above-mentioned intersections, when thermally adherable fibers are fused, each of the thermally adhesive fibers can form an adhesive through melting and solidification within 20 占 퐉 from the outermost surface.

Considering that the thermally adhesive fibers comprise a core and a sheath formed on the core, only a part of the sheath is melted and solidified when the thermally adhesive fibers are fused at the intersection, so that mutual adhesion can be formed.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to improve the process efficiency while preventing damage to the fiber by lowering the thermal bonding temperature by lowering the thermal bonding temperature and improving the bonding strength, An adhesive fiber composite can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Preparation Examples 1 to 2: Production of thermoplastic polyester elastomer resin >

Production Example 1: Polyester elastomer-I, Shore D hardness 63D

In a 75 L pilot polyester polymerization equipment equipped with a proper stirring apparatus and equipment capable of giving high vacuum so as to produce a polyester having a sufficiently high polymerization degree, 33 parts by weight of dimethyl terephthalate, 21 parts by weight of 1,4-butanediol, And 13 parts by weight of polytetramethylene ether glycol having a weight average molecular weight of 1,000, and 0.12 part by weight of tetrabutoxy titanium was added as a condensation polymerization catalyst. Then, the temperature was gradually raised from 200 ° C. to 200 ° C., 0.1 part by weight of N, N'-hexane-1,3-diylbis- (3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide) as a thermal stabilizer, 0.1 part by weight of tetrakis [ (Laurylthio) propionate] methane was added thereto, and then the temperature was raised to 250 ° C and a vacuum reaction was carried out for several hours.

The thermoplastic polyester elastomer resin obtained in Preparation Example 1 had an intrinsic viscosity of 1.25 dL / g, a glass transition temperature (Tg) of -25 캜, a melting temperature (Tm) of 212 캜, a tensile strength of 440 kg / Strength of 3,200 kg / cm 2, and flame retardancy of UL 94 HB (all combustion of specimens in the vertical combustion test).

Production Example 2: Polyester elastomer-II, Shore D hardness 40D

Except that 33 parts by weight of dimethyl terephthalate, 8 parts by weight of dimethyl isophthalate, 25 parts by weight of 1,4-butanediol, and 34 parts by weight of polytetramethylene ether glycol having a molecular weight of 1000 were added as ester forming materials, Was carried out under the same conditions as in the production of the polyester elastomer-I.

The thermoplastic polyester elastomer resin obtained in Preparation Example 2 had an intrinsic viscosity of 1.5 dL / g, a glass transition temperature (Tg) of -30 占 폚, a melting temperature (Tm) of 157 占 폚, a tensile strength of 240 kg / Strength was 645 kg / ㎠, flame retardancy was UL 94 HB (test piece burned in vertical combustion test).

≪ Preparation Examples 3 to 4: Preparation of copolyester resin >

Production Example 3: Copolyester-I

100 g of dimethyl terephthalate, 120 g of dimethyl-1,4-cyclohexanedicarboxylate, 40 g of 1,4-cyclohexanedimethanol, 40 g of 1,4-butanediol 120 g was added thereto, and the internal temperature of the reactor was gradually raised to 150 DEG C with stirring. Then, 0.1 g of tetrabutyl titanate as a catalyst was added thereto, and the temperature was raised to 235 캜 while stirring again, and the esterification reaction was continued at this temperature. When the methanol began to flow out as a reaction by-product during the reaction, the temperature of the column was maintained at 100 ° C so that the dicarboxylic acid or the dihydric alcohol component was sublimed or evaporated. When the reaction was continued for about 5 hours, the water and the methanol were not discharged any more, and the reaction product was also white opaque state, and light yellow transparent oligomer was produced, and the esterification reaction was completed.

After adding 0.3 g of antimony oxide as a catalyst to the reaction product in the oligomer state, the pressure of the reaction mixture was maintained at 1 torr by slowly evacuating slowly while keeping the reaction product from scattering, and the temperature of the reaction product was 250 ° C And the reaction was allowed to proceed for 2 hours to prepare the copolyester resin of Preparation Example 3. [ At this time, 1,4-butanediol, which is a bivalent alcohol component, was spilled out as a reaction by-product. The copolyester resin thus obtained had an intrinsic viscosity of 0.70 dl / g as measured at 30 ° C using an Ostwald viscometer and a glass transition temperature (Tg) measured using a differential scanning calorimeter of 5 ° C and a crystallization temperature Tc) was 75 ° C, and the melting temperature (Tm) was 125 ° C.

Production Example 4: Copolyester-II

50 g of dimethyl terephthalate, 30 g of dimethyl isophthalate, 20 g of adipic acid and 100 g of 1,4-butanediol were fed into a reactor equipped with a column capable of temperature control and a condenser, and the internal temperature of the reactor was adjusted to 150 Lt; 0 > C.

The copolyester resin of Production Example 4 was prepared in the same manner as in Production Example 3, and the inherent viscosity of the copolyester resin thus obtained was 0.73 dl / g as measured at 30 ° C. using an Ostwald viscometer. The glass transition temperature (Tg), the crystallization temperature (Tc) and the melting temperature (Tm) were measured by a differential scanning calorimeter at 70 ° C and 115 ° C, respectively.

≪ Examples 1 to 2: Production of thermally adhesive fiber and thermally adhesive fiber composite >

Example 1

(1) Production of thermally adhesive fibers

Using 80 g of the polyester elastomer-I of Production Example 1 as a core component, 15 g of the polyester elastomer-II of Production Example 2 and 5 g of the copolyester-I of Production Example 3 were used as sheath components, Heat-treated at a spinning temperature of 275 ° C at a spinning speed of 1,000 m / min and at a draw ratio of 3.3 times at 77 ° C, and subjected to a final heat treatment at a heat bonding temperature shown in Table 1 to obtain thermally adherable fibers. The cross-sectional area ratio of the core: sheath in the thermally adherent fiber finally produced was 80: 20, and the cross-sectional diameter was 500 탆.

 (2) Production of heat-adhesive fiber composite

The thermally adherent fibers obtained above were arranged so as to intersect with each other, and a heat-adhesive fibrous composite having a porous mesh structure including a plurality of openings was prepared through surface heat bonding between sheath portions. When the surface was thermally adhered, it was fused to a depth of about 20 m or less from the surface, based on the single heat-adhesive fiber.

Example 2

The reaction was carried out in the same manner as in Example 1 except that the copolyester-II of Preparation Example 4 was used in place of the copolyester-I of Production Example 3 as a sheath component, Fiber composite.

≪ Comparative Example: Production of thermally adhesive fiber and thermally adhesive fiber composite >

Comparative Example 1

A reaction was carried out in the same manner as in Example 1, except that 80 g of the polyester elastomer-I of Production Example 1 was used as a core component and 20 g of the polyester elastomer-II of Production Example 2 was used as a sheath component , Thermally adhesive fibers and thermally adhesive fibrous complexes were prepared.

≪ Experimental Example: Measurement of physical properties of thermally adhesive fibers obtained in Examples and Comparative Examples >

The properties of the thermally adhesive fibers obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

Experimental Example 1: Measurement of Adhesion Strength

Using the thermally adhesive fibers prepared in the above Examples and Comparative Examples, the test specimens for measurement were made to have a width of 15 mm according to ASTM D 1876, and the adhesive strength was measured using a universal testing machine (Zwick Roe 11 Z010) T-peel strength) were measured, and the results are shown in Table 1 below.

Experimental Example Results of Examples and Comparative Examples division core Cis Heat bonding temperature (캜) Adhesive strength
(g / 15 mm) Example 1 Production Example 1 Production Example 2, Production Example 3 140 750 Example 2 Production Example 1 Production Example 2, Production Example 4 135 800 Comparative Example 1 Production Example 1 Production Example 2 155 550

As shown in Table 1, the heat-bondable fibers prepared in the examples were able to be thermally adhered at a low temperature of 150 ° C or less, and the adhesive strength at that time was as high as 700 g / 15 mm or more. On the other hand, it can be confirmed that the heat-bondable fiber produced in the comparative example has a high heat bonding temperature of 155 ° C and a low bonding strength of 550 g / 15 mm.

Therefore, it is confirmed that, when the copolyester is included together with the polyester elastomer as the sheath component as in the examples, the heat bonding temperature between the core and the sheath decreases and the adhesive strength increases.

Claims (18)

A core comprising a thermoplastic polyester elastomer resin having a Shore D hardness of 55D to 90D; And
A thermosetting polyester elastomer resin formed on the core and having a Shore D hardness of 20 D to 50 D and a sheath containing a copolyester resin having a melting temperature of 80 to 150 캜.
The method according to claim 1,
Wherein the sheath has a shore D hardness of 20 D to 50 D and a thermoplastic polyester elastomer resin in which the content of the copolyester resin having a melting temperature of 80 to 150 캜 is 10 to 50 parts by weight, fiber.
The method according to claim 1,
Wherein the sheath has a melting temperature of 130 ° C to 150 ° C.
The method according to claim 1,
Wherein the copolyester resin having a melting temperature of from 80 DEG C to 150 DEG C is a residue of a diol component comprising an alicyclic diol or an aliphatic diol; And a residue of a dicarboxylic acid component including an aliphatic dicarboxylic acid or a derivative thereof, an alicyclic dicarboxylic acid or a derivative thereof, an aromatic dicarboxylic acid or a derivative thereof.
5. The method of claim 4,
Based on the whole copolyester resin, 5 to 40% by weight of the alicyclic diol, 10 to 45% by weight of an aliphatic diol, 5 to 40% by weight of an alicyclic dicarboxylic acid or a derivative thereof, 10 to 45% by weight of a carboxylic acid or a derivative thereof.
5. The method of claim 4,
From 30 to 70% by weight of the aliphatic diol, from 5 to 40% by weight of an aliphatic dicarboxylic acid or a derivative thereof and from 20 to 60% by weight of an aromatic dicarboxylic acid or a derivative thereof based on the entire copolyester resin, ≪ / RTI > by weight of the thermally adhesive fiber.
The method according to claim 1,
The thermoplastic polyester elastomer resin having Shore D hardness of 55D to 90D and the thermoplastic polyester elastomer resin having Shore D hardness of 20D to 50D each contain a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2 Thermally adhesive fiber:
[Chemical Formula 1]

In Formula 1, m is 2 to 6, X is an integer of 1 or more,
(2)

In Formula 2, n is 2 to 6, p is 10 to 30, and Y is an integer of 1 or more.
8. The method of claim 7,
Wherein the thermoplastic polyester elastomer resin having a Shore D hardness of 55D to 90D comprises less than 12 mol% of the repeating unit represented by the formula (2) as a whole resin.
8. The method of claim 7,
Wherein the thermoplastic polyester elastomer resin having a shore D hardness of 20D to 50D comprises at least 12 mol% of the repeating unit represented by the above formula (2) relative to the total resin.
The method according to claim 1,
Wherein the content of the thermoplastic polyester elastomer resin having a Shore D hardness of 20D to 50D is 1 to 50 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer resin having the Shore D hardness of 55D to 90D.
The method according to claim 1,
Wherein the core has an average cross-sectional diameter of 80 mu m to 400 mu m and an average cross-sectional diameter of the sheath of 20 mu m to 100 mu m.
The method according to claim 1,
Wherein the copolyester resin having a melting point of from 80 캜 to 150 캜 has an intrinsic viscosity of from 0.2 dl / g to 0.9 dl / g.
The method according to claim 1,
The copolyester resin having a melting temperature of 80 to 150 캜 has a glass transition temperature (measured by DSC) of -30 캜 to 10 캜 and a crystallization temperature (measured by DSC) of 50 캜 to 80 캜. Adhesive fiber.
The method according to claim 1,
Heat-adhesive fibers used in the material of chairs, sneakers, curtains, car mats.
A thermally adhesive fiber composite comprising the thermally adhesive fiber of claim 1.
16. The method of claim 15,
Wherein the thermally adhesive fibrous composite comprises a thermally adhesive fibrous cross-section of a porous mesh structure.
17. The method of claim 16,
Thermally adherable fiber cross-linked, wherein the thermally adhesive fiber is fused at each crossing point in the thermally adhesive fiber cross-product.
18. The method of claim 17,
Bonded at a depth of 20 占 퐉 or less from the outermost surface of the thermally adhesive fiber.