KR101856141B1 - Low melting Polyester resin having a Stretch ability - Google Patents
Low melting Polyester resin having a Stretch ability Download PDFInfo
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- KR101856141B1 KR101856141B1 KR1020160155866A KR20160155866A KR101856141B1 KR 101856141 B1 KR101856141 B1 KR 101856141B1 KR 1020160155866 A KR1020160155866 A KR 1020160155866A KR 20160155866 A KR20160155866 A KR 20160155866A KR 101856141 B1 KR101856141 B1 KR 101856141B1
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- polyester resin
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- low melting
- point polyester
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- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a low melting point polyester resin having elasticity formed by a hard segment and a soft segment, wherein the hard segment includes dicarboxylic acid composed of dimethyl terephthalate (DMT) and 30 to 70 mol% (BG), 30 to 70 mol% of hexylene glycol (HG), and the soft settable material is a polytetramethyleneglycol (PTMG) Methylene glycol (PTMG) relates to a low melting point polyester resin having elasticity contained in an amount of 30 to 60% by weight of a low melting point polyester resin having elasticity.
Description
The present invention relates to a low-melting-point polyester resin having elasticity, a low-melting-point polyester resin capable of melting at a low temperature and excellent in stretchability and having stretchability suitable for a film.
Adhesives used in apparel and fabrics are indispensable auxiliary materials that must be used in order to improve the appearance of clothes. The purpose of use is to improve the productivity by shortening the bonding and manufacturing process of the release type fabrics and uniformizing the finished products. The explosive growth of the outdoor and sports apparel market is leading to the development of adhesives with elasticity that provide good fit and comfortable fit.
Korean Patent No. 1558713 discloses a process for producing a low melting point thermoplastic polyurethane film having a first adhesive layer of thermoplastic polyurethane capable of bonding at a low temperature at a minimum temperature of 110 ° C and a second adhesive layer composed of an aromatic based hot melt thermoplastic polyurethane It is introduced.
In Korean Patent No. 1098885, thermoplastic polyurethane is sequentially laminated between hot melt adhesive film layers to prevent the occurrence of breakage of the adhesive interface in the adhesive layer even when adhered, so that the thermoplastic Polyurethane hot melt adhesive film is introduced.
However, there is a disadvantage that the adhesive film or adhesive composition applied in these conventional technologies is not cut by a plotter cutter because the components thereof are mostly hot-melt thermoplastic polyurethane resin, which is an adhesive film. Therefore, it is necessary to cut with a laser cutter, which is expensive equipment, and there is a problem that it is burned or yellowing occurs.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the problems of the prior art, and it is an object of the present invention to provide a low melting point polyester resin having adhesive property at a temperature lower than the melting point of a co- .
It is another object of the present invention to provide a low-melting-point polyester resin which can be molded at a low temperature and is excellent in stretchability and has elasticity suitable for an elastic film.
It is another object of the present invention to provide a film containing a low-melting-point polyester resin having elasticity according to the present invention, which is easy to manufacture and which can use a plotter cutter.
The present invention relates to a low melting point polyester resin having elasticity formed by a hard segment and a soft segment, wherein the hard segment includes dicarboxylic acid composed of dimethyl terephthalate (DMT) and 30 to 70 mol% (BG), 30 to 70 mol% of hexylene glycol (HG), and the soft settable material is a polytetramethyleneglycol (PTMG) Methylene glycol (PTMG) is contained in an amount of 30 to 60% by weight based on the weight of the low-melting-point polyester resin having elasticity.
The dicarboxylic acid to the hard segment may further contain isophthalic acid (IPA) or a derivative thereof. The isophthalic acid (IPA) or a derivative thereof may be contained in an amount of 1 to 30 mol% And a low melting point polyester resin having elasticity.
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The low-melting-point polyester resin having elasticity has a stretchability of 200% or more. The low-melting-point polyester resin has elasticity.
Wherein the low melting point polyester resin having elasticity has a melt temperature (Tm) of 80 to 130 占 폚.
The low-melting-point polyester resin having elasticity has an elastic viscosity (IV) of 1.2 to 2.0. The polyester resin has elasticity.
The present invention also provides a film comprising a low-melting-point polyester resin having the stretchability described above.
The low melting point polyester resin having elasticity according to the present invention has a low melting point, easy control of the melting point, and an effect of having a stretchability of 200% or more.
Further, the film comprising a low melting point polyester resin having elasticity of the present invention has an effect of being suitable for use in a film for clothes due to its low temperature adhesiveness, which is superior to conventional polyurethane materials.
In addition, the cutting property using the plotter cutter is excellent, and the speed of the work process due to the work at the low temperature can be expected to be improved.
1 is a view showing a method of evaluating an adhesion force.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, it should be noted that, in the drawings, the same components or parts have the same reference numerals as much as possible. 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 low melting point polyester resin having elasticity formed by a hard segment and a soft segment.
The hard segment is formed of a diol component composed of dicarboxylic acid composed of dimethyl terephthalate (DMT), butylene glycol (BG), and hexylene glycol (HG).
The soft settler is formed of a polyol, Polytetramethyleneglycol (PTMG).
As described above, the stretchable low-melting-point polyester resin of the present invention, which is formed of a hard segment and a soft segment, is an elastomer resin having excellent elasticity.
As the hard segment, it is preferable to use a diol component composed of dicarboxylic acid of dimethyl terephthalate (DMT), 30 to 70 mol% of butylene glycol (BG) and 30 to 70 mol% of hexylene glycol (HG) something to do.
The dicarboxylic acid may further contain isophthalic acid (IPA) or a derivative thereof in order to control the melting point and the intrinsic viscosity (IV) of the low melting point polyester resin to be produced.
When the content of isophthalic acid (IPA) or a derivative thereof is greater than 30 mol% of the dicarboxylic acid component, the melting point of the low melting point polyester resin may be too low , It is preferable that the isophthalic acid (IPA) or its derivative contains 1 to 30 mol% of the dicarboxylic acid component.
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By using isophthalic acid (IPA) or a derivative thereof as described above, the melting point can be controlled while maintaining the elastic properties and the physical properties of the low melting point polyester resin having elasticity according to the present invention.
The dicarboxylic acid and the diol may preferably be used in a molar ratio of 0.8: 1.0 to 1.0: 1.5.
It is preferable that the polytetramethylene glycol (PTMG) forming the soft settable material is contained in an amount of 30 to 60% by weight of the weight of the low melting point polyester resin having elasticity.
Conventional polyesters use aromatic or aliphatic dicarboxylic acids such as adipic acid and succinic acid as a copolymerization raw material in order to control the melting point. In the present invention, dimethyl terephthalate (DMT) and isophthalic acid (IPA) (BG) and hexylene glycol (HG) as diol components, it is possible to easily control various melting points required in the bonding process of the final product while maintaining elasticity and physical properties.
The melting point can be controlled according to the content of hexylene glycol (HG) in the diol component. As the content ratio of hexylene glycol increases by 1 mol%, the melting point of the resin decreases by 1.625 ° C, And the melting point of hexylene glycol can be defined by the following equation.
<Relation>
Change in melting point of polyester resin (占 폚) = - 1.625 占 mole% of hexylene glycol
(0? Hexylene glycol composition mole%? 65)
When the content of the hexylene glycol (HG) is 65 mol% or more, the effect of controlling the melting point is lost.
The soft set includes polytetramethyleneglycol (PTMG), which is a polyol. It is used in combination with butylene glycol (BG) and hexylene glycol (HG) used as a diol component in the hard segment. Thereby making it possible to produce copolymerized polyesters having various melting points while maintaining their physical and elastic properties.
The polytetramethylene glycol (PTMG) preferably has a number average molecular weight in the range of 400 to 20,000, and polytetramethylene glycol having a different molecular weight within the molecular weight range may be used singly or in combination.
The low melting point polyester resin having elasticity according to the present invention can be obtained by esterifying a hard segment of dimethyl terephthalate (DMT), butylene glycol (BG), hexylene glycol (HG) and soft segment polytetramethylene glycol (PTMG) An esterification step in which the polymerization reaction is carried out in the presence of a polymerization catalyst, a heat stabilizer, a light stabilizer and the like.
The esterification step may be carried out by reacting dimethyl terephthalate (DMT) of dicarboxylic acid with butylene glycol (BG), hexylene glycol (HG), and diethylene glycol to form a hard segment of the low melting point polyester- The soft segment polytetramethylene glycol is esterified.
Preferably, dimethyl terephthalate (DMT), butylene glycol (BG), hexylene glycol (HG), and soft segment polytetramethylene glycol in the hard segment are added together with the esterification reaction catalyst into a heat resistant pressure vessel, The reaction is carried out to prepare an oligomer solution.
The dicarboxylic acid may further contain isophthalic acid (IPA) or a derivative thereof.
The dicarboxylic acid and the diol in the hard segment are synthesized at a molar ratio of 1: 1. To increase the stability and speed of the reaction, the dicarboxylic acid and the diol are mixed at a molar ratio of 1: 1.2 to 1.5, It is preferable to carry out the reaction.
Examples of the catalyst used in the esterification step include acetic acid-based catalysts such as zinc acetate, sodium acetate and magnesium acetate, and titanium catalysts such as tetranormalbutoxy titanate, tetraisopropyl titanate, titanium oxide / silica oxide microcopolymer and nano- Based catalyst. These catalysts may be used alone or in combination of two or more.
In the esterification step, the catalyst may be added in the range of 50 to 1000 ppm, preferably in the range of 200 to 700 ppm, based on 100 parts by weight of the low melting point polyester resin having elasticity.
If the amount of the catalyst is insufficient, the esterification reaction rate may be slowed, and the thermal stability of the low melting point polyester resin may be lowered. The reaction temperature of the heat-resistant, pressure-resistant vessel in which the esterification reaction proceeds to distill methanol produced as a by-product is preferably in the range of 150 to 210 ° C.
The polycondensation step is carried out in a pressure-resistant / heat-resistant reactor which can be vacuum-decompressed together with an oligomer solution obtained by the esterification reaction and soft segment polytetramethylene glycol, a condensation polymerization catalyst, a heat stabilizer and a photo- (BG) and hexylene glycol (HG) were distilled at a pressure of 200 to 270 DEG C and then the condensation polymerization was completed under a high degree of vacuum of 1 mmHg or less to obtain an ethylene- A melting point polyester resin can be produced.
Examples of the catalyst used in the condensation polymerization step include antimony catalysts such as antimony trioxide and antimony acetate or titanium catalysts such as tetranomal butoxytitanate, tetraisopropyl titanate, titanium oxide / silica oxide microcopolymer and nano titanate Ti) based catalyst is preferably used.
The polycondensation catalyst is added in the range of 50 to 2000 ppm with respect to 100 parts by weight of the low melting point polyester resin, preferably in the range of 300 to 1200 ppm.
If the amount of the catalyst is insufficient in the condensation polymerization step, the rate of the condensation polymerization may be slowed, and the physical properties of the low melting point polyester resin may be deteriorated, and the thermal stability of the low melting point polyester resin may be decreased.
As described above, the stretchable low melting polyester resin of the present invention has a stretchability of 200% or more and has a low melting point characteristic at a melting temperature (Tm) of 80 to 130 캜.
In addition, the low-melting-point polyester resin having elasticity may be suitably used as a raw material for an injection-molded product or a film molded product having various intrinsic viscosities (IV) of 1.2 to 2.0.
Hereinafter, examples of the method for producing a low melting point polyester resin having elasticity according to the present invention are shown, but the present invention is not limited to the examples.
Example One
14.5 kg of dimethyl terephthalate (DMT) as dicarboxylic acid, 0.6 kg of isophthalic acid, 3.0 kg of butylene glycol (BG) as diol component, 6.4 kg of hexylene glycol (HG), 7.5 kg of polytetramethylene glycol (PTMG) 9 g of tetra-n-butoxytitanate as an oxidation reaction catalyst was added to a stirrerable 100 L heat and pressure reactor and heated and stirred at an initial temperature of 130 ° C to confirm that dimethyl terephthalate (DMT) melted and melted in the diol component do.
After confirming that the dimethyl terephthalate (DMT) was melted and dissolved, the reaction was continued for 4 hours with heating and stirring until the inner temperature of the reactor was gradually elevated to 205 ° C. Methanol generated as a byproduct was distilled out from the reactor and removed, .
The oligomer solution formed in the esterification reaction was added to a heat resistant and pressure resistant 100 liter reactor capable of vacuum decompression and stirring, and then 125 g of a heat stabilizer (Song 1330), 125 g of a light stabilizer (UV 70) Add 20 g of tanate.
The polycondensation reaction was first slowly reduced and heated, and the condensation polymerization was completed under a high vacuum at a final temperature of 250 ° C and a final vacuum degree of 1 mmHg or less to prepare a low melting point polyester resin having elasticity according to the present invention.
The mol% of the compound and the compound used in Example 1 are shown in Table 1.
Example 2 to 6
But the content of dimethyl terephthalate (DMT) isophthalic acid (IPA) butylene glycol (BG) hexylene glycol (HG) and polytetramethylene glycol (PTMG) Was prepared. ≪ tb > < TABLE >
The molar percentages of the compounds and compounds used in Examples 2 to 5 are shown in Table 1.
Comparative Example 1 to 3
Adipic acid (AA) and succinic acid (SA) were used in the dicarboxylic acid, and the polyester resin was prepared by varying the content of the diol component.
The molar percentages of the compounds and compounds used in Comparative Examples 1 to 3 are shown in Table 1.
Comparative Example 4
General polyurethane materials for film were purchased, and adhesive force, film cutting property, and physical properties were analyzed.
◈ Evaluation of physical properties of examples and comparative examples
The melting point, intrinsic viscosity, stretchability and adhesion of the above Examples 1 to 6 and Comparative Examples 1 to 4 were measured and evaluated. The measurement method is as follows.
In Comparative Example 4, a general polyurethane material for a film was purchased and measured.
◎ Melting point: Measured using a Perkin Elmer (DSC-Diamond), and when there is no heat absorption peak (no melting point), a dynamic thermal characteristic analyzer (Perkin Elmer, DMA-7, TMA mode ) Was used to measure the softening behavior.
Intrinsic Viscosity (IV): Copolymer polyester was dissolved in phenol / tetrachloroethane (weight ratio 50/50) to make a 0.5 wt% solution, and the viscosity was measured at 35 캜 by a Uvold viscometer.
⊚ Adhesion: A sample was prepared in the form of a film in Examples and Comparative Examples, a sample was placed between the fabrics (substrates) as shown in FIG. 1, hot-pressed at a predetermined pressure and temperature by a hot press, Tensile Testing of Thin Plastic Sheeting.
◎ Tensile elongation: The film was cut into 1 inch width and 15 cm length after preparation of the film by polymerizing chip, and the stretching length was measured by Instron's 4467 Series.
Tensile elongation formula = ((extended length) / (initial length)) x 100
◎ Film Cutting: Mimaki-Holder products of Mimaki Co., Ltd. were manufactured after glitter sheet production.
Crystallization time: Measured using a thermal differential scanning calorimeter (Perkin Elmer, DSC-Diamond), and the heat absorption crystallization peak time was measured at 70 ° C for 1 hour under isothermal conditions.
unit
time
(kgf / in)
As shown in Table 2, crystallization times of the polyesters of Examples 1 to 6 and Comparative Examples 1 to 3 were compared with each other to confirm that crystallization time was shortened by the presence of hexylene glycol (HG).
The comparison of the cuttability of Plotter Cutter after the production of the films of Examples 1 to 6 and Comparative Example 4 shows that the urethane material is not cut while the film made of the low melting point polyester resin of the present invention is cut by a plotter cutter Respectively.
Further, it was confirmed through comparison between Examples 1 to 6 and Comparative Example 3 that as the weight percentage of the soft segment polytetramethylene glycol increases, the hardness decreases and the stretchability improves.
As in Example 6, it was confirmed that the polyester resin of the present invention can have thermal adhesiveness at 80 캜 which is a temperature lower by 30 캜 than that of the polyurethane material of Comparative Example 4.
In addition, it was confirmed that the melting point of the polyester resin of Examples 1 to 6 was lowered by 1.625 ° C as the content ratio of hexylene glycol (HG) was increased by 1 mol%, and the low melting point polyester Based resin has an advantage that various melting points required in the molding process of the final product can be easily controlled while maintaining elasticity and physical properties.
Claims (7)
Examples of the hard segment include dicarboxylic acid composed of dimethyl terephthalate (DMT), 30 to 70 mol% of butylene glycol (BG), 30 to 70 mol% of hexylene glycol (HG) ≪ / RTI >
The soft segment may be polytetramethyleneglycol (PTMG)
The polytetramethylene glycol (PTMG) is a low-melting-point polyester resin which is contained in an amount of 30 to 60 wt% of the weight of the low-melting-point polyester resin having elasticity. The polytetramethylene glycol has a stretchability of not less than 200% Polyester resin.
The dicarboxylic acid to the hard segment may further contain isophthalic acid (IPA) or a derivative thereof. The isophthalic acid (IPA) or a derivative thereof may be contained in an amount of 1 to 30 mol% Wherein the low melting point polyester resin has elasticity.
The low melting point polyester resin having elasticity has a melt temperature (Tm) of 80 to 130 占 폚.
The low melting point polyester resin having elasticity has an intrinsic viscosity (IV) of 1.2 to 2.0.
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| KR1020160155866A KR101856141B1 (en) | 2016-11-22 | 2016-11-22 | Low melting Polyester resin having a Stretch ability |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930008207B1 (en) * | 1989-12-22 | 1993-08-26 | 삼성전관 주식회사 | Process for production of alkaline earth sulfur phosphor |
| JP2002080813A (en) * | 2000-06-27 | 2002-03-22 | Tokai Rubber Ind Ltd | Adhesive composition and insulating tape for flat cable using this |
| JP2010285576A (en) * | 2009-06-15 | 2010-12-24 | Ichikin:Kk | Thermoplastic resin composition |
| KR101457519B1 (en) * | 2012-12-07 | 2014-11-03 | 도레이케미칼 주식회사 | A cushion using elastic nonwoven fabric |
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2016
- 2016-11-22 KR KR1020160155866A patent/KR101856141B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930008207B1 (en) * | 1989-12-22 | 1993-08-26 | 삼성전관 주식회사 | Process for production of alkaline earth sulfur phosphor |
| JP2002080813A (en) * | 2000-06-27 | 2002-03-22 | Tokai Rubber Ind Ltd | Adhesive composition and insulating tape for flat cable using this |
| JP2010285576A (en) * | 2009-06-15 | 2010-12-24 | Ichikin:Kk | Thermoplastic resin composition |
| KR101457519B1 (en) * | 2012-12-07 | 2014-11-03 | 도레이케미칼 주식회사 | A cushion using elastic nonwoven fabric |
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