KR20170075436A - Thermal adhesive co-polyester resin and binder fiber including the same - Google Patents
Thermal adhesive co-polyester resin and binder fiber including the same Download PDFInfo
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- KR20170075436A KR20170075436A KR1020150185083A KR20150185083A KR20170075436A KR 20170075436 A KR20170075436 A KR 20170075436A KR 1020150185083 A KR1020150185083 A KR 1020150185083A KR 20150185083 A KR20150185083 A KR 20150185083A KR 20170075436 A KR20170075436 A KR 20170075436A
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- South Korea
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- polyester resin
- thermosetting
- acid
- component
- copolymerizable
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Abstract
The present invention relates to an acidic component comprising terephthalic acid or an ester-forming derivative thereof; And 1,3-benzene diol (Resorcinol) and ethylene glycol, which is excellent in thermal adhesion at a low process temperature and maintains an adhesive force even at a high temperature, and is excellent in shape stability, and a thermosetting copolymerizable polyester resin Binder fibers.
Description
The present invention relates to a thermoadhesive copolymerizable polyester resin and a binder fiber containing the same, and relates to a thermoadhesive copolymerizable polyester resin excellent in shape stability by maintaining an adhesive force even at high temperatures and a binder fiber containing the same.
The thermally fusible binder fibers used to bond the filaments or staple fibers constituting the web or sheet of the nonwoven fabric should have a glass transition temperature close to that of a regular polyethylene terephthalate fiber with a heat bonding temperature of 140 to 150 ° C To do this, it is necessary to eliminate the crystal structure in the polymer and make the polymer structure into an amorphous form.
For this purpose, it is typical to copolymerize terephthalic acid with isophthalic acid as a copolymerization component in the synthesis of polyester resin, wherein isophthalic acid is added in an amount of 20 to 45 mol% based on the ester molar amount, and the polyester resin thus synthesized is amorphous And has a final melting point ranging from 145 to 180 ° C and can be used as a polyester fiber for a binder. However, in the polyester resin for a binder using isophthalic acid, a cyclic compound having a degree of polymerization of 2 to 3 is formed when synthesized, and the melting point of the cyclic compound is about 325 DEG C and is not melted at the polyester spinning temperature, Thereby shortening the cycle of exchanging the pack, and the price of isophthalic acid is usually high. In addition, diethylene glycol can be used as a copolymerization material. Polyester resin synthesized by copolymerization of diethylene glycol has a high glass transition temperature, which is problematic in the stretching process, product fusing between fibers during product transportation or dropping, Strength is low.
U.S. Patent No. 4,129,675 discloses a low melting point polyester binder based on terephthalic acid and isophthalic acid, but it is uneconomical because it requires a temperature of 190 ° C or more in thermal bonding.
U.S. Patent No. 4,166,896 discloses a method for producing an unsaturated polyester by copolymerizing unsaturated dicarboxylic acid or the like with a low-molecular-weight water having depolymerized polyester, but the fiber according to the patent also has low economic efficiency, There is a disadvantage that it is excessively high melting point and high crystallinity.
U.S. Patent No. 4,065,439 discloses a low melting point polyester obtained using terephthalic acid / isophthalic acid / adipic acid (or sebacic acid) and ethylene glycol / neopentyl glycol, but the melting point of the binder is 45 ° C to 60 ° C It is not only difficult to use as a garment wick but also has low dimensional stability under high temperature conditions.
On the other hand, Korean Patent Laid-Open Publication No. 2001-11548 discloses a polyester resin composition comprising a dicarboxylic acid component of terephthalic acid and a phthalic anhydride, and a diol component of ethylene glycol and diethylene glycol, which are excellent in adhesion to polyester, Although the binder for ester-based fibers is provided, the binder is complicated in the reaction mechanism by directly using anhydrous phthalic acid, and thus has a disadvantage in that the condensation polymerization temperature must be lowered in order to prevent the problem of poor color of the copolymer polyester. In addition, such a low temperature polycondensation reaction has a problem in that the productivity is lowered.
That is, the copolyester synthesized using the phthalic anhydride of Korean Patent Laid-Open No. 2001-11548 is obtained under the same condition as the polyethylene terephthalate polycondensation step in which the copolymer polyester is heated to 270 ° C to 290 ° C under a reduced pressure of 1 mmHg or lower There is a disadvantage that the color of the polymer becomes poor. This is because the phthalic anhydride charged in the composition of the reaction system under the high temperature and high vacuum polymerization conditions participates in the reaction in the state where the ring-opening reaction, the direct esterification reaction and the transesterification reaction are mixed in the reaction process to generate pyrolysis and side reactions, Because.
DISCLOSURE OF THE INVENTION The present invention was made to solve the problems of the prior art as described above, and it is an object of the present invention to provide a thermoplastic resin composition which is obtained by copolymerizing 1,3 benzenediol having a high boiling point with a polyester resin, Which is excellent in heat resistance, and maintains an adhesive force even at a high temperature, and is excellent in shape stability.
Another object of the present invention is to provide an adhesive copolymerizable polyester binder fiber formed through the adhesive copolymerizable polyester resin.
The present invention relates to an acidic component comprising terephthalic acid or an ester-forming derivative thereof; And 1,3-benzenediol (Resorcinol), and ethylene glycol. The thermosetting copolymerizable polyester resin according to claim 1,
Also, the 1,3-benzenediol is copolymerized in an amount of 10 to 50 mol% based on the molar amount of the copolymerized polyester resin.
The present invention further provides a thermoadhesive copolymerizable polyester resin characterized in that the diol component further comprises diethylene glycol and the diethylene glycol is copolymerized in an amount of 1 to 25 mol% based on the mole of the copolymerized polyester resin .
Wherein the thermosetting copolymerizable polyester resin is further copolymerized with a multifunctional component for strengthening intermolecular bonding of the thermosetting copolymerizable polyester resin.
The polyfunctional component may be at least one selected from the group consisting of trimethylolpropane, trimellitic acid, trimesic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, Wherein the thermosetting copolymerizable polyester resin is at least one selected from the group consisting of glycerin, pentaerythritol, and sorbitol.
Further, there is provided a thermally adhesive copolyester binder fiber characterized by containing the thermoadhesive copolymerizable polyester resin.
The heat adhesive copolymerizable polyester binder fiber is formed in a sheath-core type, and the core component is a general polyester resin and the sheath component is formed of a thermoadhesive copolymerizable polyester resin. Polyester binder fibers.
The thermosetting copolymerizable polyester resin according to the present invention as described above has a glass transition temperature which is not much lower than that of a general polyester resin, has excellent thermal adhesion at a low process temperature, maintains an adhesive force even at a high temperature, have.
Further, the thermally adhesive copolyester binder fiber including the thermoadhesive copolymerizable polyester resin is excellent in durability and shape stability in a high-temperature atmosphere exposed to the sun for a long time in the outdoor, such as an automotive interior headliner product The strength is maintained and the molding nonwoven fabric has an effect of preventing the sagging phenomenon under a high temperature atmosphere.
Hereinafter, a preferred embodiment of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.
As used herein, the terms " about, " " substantially, " " etc. ", when used to refer to a manufacturing or material tolerance inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.
The present invention relates to a thermoadhesive copolymerizable polyester resin formed from an acid component comprising terephthalic acid or an ester-forming derivative thereof, and a diol component composed of 1,3-benzenediol (Resorcinol) and ethylene glycol.
[Chemical Formula 1]
The above 1,3 benzenediol is a compound having the structure as shown in formula (1). When a resin is prepared by using 3 benzene diols, it has an aromatic ring structure to widen the free space between the main chains and to react with the ester with the diol component (II), which has a higher reactivity than that of isophthalic acid (IPA) due to its aromatic structure. Therefore, it functions very effectively in lowering the melting temperature of the polymer and destroying crystallinity.
On the other hand, as the effect of lowering the melting temperature relative to the amount of the injection is larger, the lower the effect of lowering the glass transition temperature, the more effective the copolymerization component. In the case of the 1,3 benzenediol, the effect of lowering the melting temperature is large, The glass transition temperature is 65 DEG C or higher even in the state of becoming an amorphous polymer.
Therefore, it not only enables thermal bonding between fibers even at a low process temperature, but also has excellent form stability even at a high temperature of 100 to 130 DEG C after the production of the nonwoven fabric. In addition, since the thermal property is superior to isophthalic acid, even if a small amount of isophthalic acid is used, the production cost can be lowered because the same effect can be obtained.
It is preferable that the 1,3 benzenediol is copolymerized in an amount of 10 to 50 mol% based on the molar amount of the copolymer polyester resin.
If the content of the 1,3-benzenediol is less than 10 mol%, the melting point is not sufficiently lowered to obtain a desired polyester resin. When the content of the 1,3-benzenediol is less than 10 mol%, a desired effect can not be obtained. On the contrary, when the amount is excessively increased, excessive melting point lowering may cause adverse effects such as fusion and adhesion between adjacent fibers.
In order to further lower the melting point of the thermoadhesive copolymerizable polyester resin, diethylene glycol (DEG) may be further copolymerized as the diol component.
If the content of the diethylene glycol is too high, the melting point and the glass transition temperature may be too low. If the content is too low, the effect of lowering the melting point may be insignificant, so that the content of the diethylene glycol is 1 to 25 mol% based on the molar amount of the copolymerized polyester resin Lt; / RTI >
In order to enhance intermolecular bonding of the thermoadhesive copolymerizable polyester resin of the present invention, a polyfunctional component may be further copolymerized and copolymerized.
The polyfunctional component is preferably selected from the group consisting of a polycarboxylic acid, a polyol and a polyoxycarboxylic acid. In particular, the polyfunctional component is preferably selected from the group consisting of trimethylolpropane, trimellitic acid, trimesic acid, 3,3 ', 4,4'- Tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and derivatives thereof, glycerin, pentaerythritol, and sorbitol.
As described above, the thermoadhesive copolyester binder fiber can be produced through the thermoadhesive copolymerizable polyester resin according to the present invention containing 1,3 benzenediol.
When the thermoadhesive copolymerizable polyester binder fiber is produced by the thermoadhesive copolymerizable polyester resin of the present invention, there may be restrictions on the use due to physical problems. Therefore, a general polyester resin such as polyethylene terephthalate resin, .
When the thermosetting copolymerizable polyester binder fiber is formed in the form of the composite fiber, it is preferably formed into a sheath-core type, and the core component is a general polyester resin and the sheath component is formed of a thermoadhesive copolymerizable polyester resin Lt; / RTI >
The thermally adhesive copolyester binder fiber according to the present invention as described above can be thermally adhered at a low temperature in a range similar to the temperature applied to conventional binder fibers, Even if the durability and form stability are required in a high temperature atmosphere exposed to the sun for a long time in the outdoor, such as a liner product, the strength is maintained and the molding nonwoven fabric can prevent sagging under a high temperature atmosphere.
Hereinafter, examples of the method for producing the thermoadhesive copolymerizable polyester resin according to the present invention are shown, but the present invention is not limited to the examples.
Example 1 to 4
Terephthalic acid and ethylene glycol were added to the ester reaction tank and reacted at a temperature of 258 ° C by a conventional method to prepare an oligomer having a 96% reaction rate.
An esterified oligomer was prepared by introducing an acid component, 1,3-benzenediol (Resorcinol) based on the molar amount of polyethylene terephthalic acid, into the oligomer, and transesterifying at 250 DEG C in the presence of a conventional transesterification catalyst.
The esterification oligomer was charged with a conventional polycondensation catalyst, and the temperature was elevated to 280 DEG C while gradually reducing the pressure so that the final reduced pressure was 0.1 mmHg, thereby conducting a condensation polymerization reaction. Thus, the thermoadhesive copolymerizable polyester resin of the present invention .
The copolymerization components and contents of Examples 1 to 4 are shown in Table 1.
Example 5 to 8
Polymerization was carried out under the same conditions as in Examples 1 to 4 except that 10 mol% of diol diethylene glycol (DEG) having a boiling point of less than 300 DEG C was added.
The copolymerization components and contents of Examples 5 to 8 are shown in Table 1.
Comparative Example 1 to 4
Polymerization was carried out under the same conditions as in Examples 1 to 4, except that isophthalic acid instead of 1,3-benzenediol (Resorcinol) was added in amounts.
The copolymerization components and contents of Comparative Examples 1 to 4 are shown in Table 1.
Comparative Example 5 to 8
Polymerization was carried out under the same conditions as in Comparative Examples 1 to 54 except that 10 mol% of DEG as a diol having a boiling point of less than 300 DEG C was added.
The copolymerization components and the contents of Comparative Examples 5 to 8 are shown in Table 1.
◈ Measurement of physical properties of examples and comparative examples
The properties of the copolyester resins of Examples 1 to 8 and Comparative Examples 1 to 8 prepared above were measured.
1. Measurement of cyclic compound content
The mole percentage of the additive of the copolymer polyester was determined by dissolving the copolymer polyester in trifluoroacetic acid and using a DRX-300 proton nuclear magnetic resonance apparatus (1 H NMR) of Bruker.
2. Measurement of Melting Point / Glass Transition Temperature and Softening Behavior
(Perkin Elmer, DMA-7; TMA mode) when there is no heat absorption peak, that is, when no melting point is present, by using a thermal differential scanning calorimeter (Perkin Elmer, DSC-7) The softening behavior was measured.
3. Measurement of intrinsic viscosity (IV)
The copolymerized polyester was dissolved in phenol / tetrachloroethane (weight ratio 50/50) to make a 0.5 wt% solution, and then measured at 35 캜 with a Ubbelohde viscometer.
4. Adhesion at room temperature
The heat-sealable nonwoven fabric thus prepared was fixed at a density of 2 g / 100 cm 2, and the low temperature bonding strength was measured at a temperature of 75 ° C. by the method of ASTM D1424.
As shown in Table 2, when Examples 1 to 4 using 1,3-benzenediol (Resorcinol) were compared with Comparative Examples 1 to 4 using isophthalic acid, they had an intrinsic viscosity of at least about the same, It has a high effect of lowering the melting temperature and has a glass transition temperature of 65 ° C or higher.
As can be seen from the results of the room temperature adhesion strength, it can be seen that the adhesion strength was excellent in Examples 3 to 4 in which 1,3-benzenediol (Resorcinol) was used in a certain amount.
When copolymerized with diethylene glycol, the glass transition temperature is high and the adhesive strength at room temperature is relatively low. In this case, as in Examples 5 to 8, 1,3-benzene diol (Resorcinol) As compared with the copolymerization with isophthalic acid as in Comparative Examples 5 to 8, it can be understood that they have a relatively high adhesion strength.
Therefore, the use of 1,3-benzenediol as a copolymerization component has the effect of improving the physical properties and the production cost of the polyester resin for a binder.
Claims (7)
Wherein the 1,3-benzenediol (Resorcinol) is copolymerized in an amount of 10 to 50 mol% based on the molar amount of the copolymerized polyester resin.
Wherein the diol component further comprises diethylene glycol, and the diethylene glycol is copolymerized in an amount of 1 to 25 mol% based on the molar amount of the copolymer polyester resin.
Wherein the thermosetting copolymerizable polyester resin is further copolymerized with a multifunctional component for strengthening intermolecular bonding of the thermosetting copolymerizable polyester resin.
The polyfunctional component may be at least one selected from the group consisting of trimethylolpropane, trimellitic acid, trimesic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, Glycerin, pentaerythritol, and sorbitol. The thermosetting copolymerizable polyester resin according to claim 1, wherein the thermosetting copolymerizable polyester resin is at least one selected from the group consisting of glycerin, pentaerythritol, and sorbitol.
Wherein the thermosetting copolymerizable polyester binder fiber is formed into a sheath-core type, the core component is a general polyester resin, and the sheath component is formed of a thermosetting copolymerizable polyester resin. fiber.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150185083A KR101807001B1 (en) | 2015-12-23 | 2015-12-23 | Thermal adhesive co-polyester resin and binder fiber including the same |
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| KR1020150185083A KR101807001B1 (en) | 2015-12-23 | 2015-12-23 | Thermal adhesive co-polyester resin and binder fiber including the same |
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| KR20170075436A true KR20170075436A (en) | 2017-07-03 |
| KR101807001B1 KR101807001B1 (en) | 2017-12-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20230022649A (en) * | 2021-08-09 | 2023-02-16 | 도레이첨단소재 주식회사 | Polyester resin, preparing method thereof, thermally adhesive polyester fiber made thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102117688B1 (en) * | 2018-04-06 | 2020-06-02 | 주식회사 휴비스 | Polyester fiber using binder Having Advanced Adhesive Strength |
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| JP2000044665A (en) | 1998-07-27 | 2000-02-15 | Kanebo Ltd | Polyester resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20230022649A (en) * | 2021-08-09 | 2023-02-16 | 도레이첨단소재 주식회사 | Polyester resin, preparing method thereof, thermally adhesive polyester fiber made thereof |
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