KR101288416B1 - Composition for producing flame retardant polyester yarns - Google Patents

Abstract

A composition for use in the manufacture of flame retardant polyester yarns comprising from about 93 to 99.5 weight percent polyester, from about 0.25 to 4 weight percent chain extender, and from about 0.25 to 3 weight percent polyoxyalkyleneamine.

Description

Composition for making flame retardant polyester yarn {COMPOSITION FOR PRODUCING FLAME RETARDANT POLYESTER YARNS}

This application is related to Provisional Application Serial No. 60 / 657,734, filed March 3, 2005, which claims priority.

Background and Field of the Invention

The present invention relates generally to polyester yarns used in the manufacture of fabrics and floorings, and more particularly to compositions for making such yarns which provide yarns with improved fire retardancy.

It is very important for products such as fabrics and floorings made of polyester fibers to exhibit sufficient flame retardancy in accordance with modern regulations. We have invented a novel composition which is very effective and economical in the provision of fibers of flame retardant polyester used in the manufacture of fabrics and floorings, or yarns that retain their other desirable physical properties.

Summary of the Invention

According to the invention, the composition for the production of polyester based yarns with improved flame retardancy comprises polyester, at least one polyoxyalkylenediamine and at least one chain extender. Preferably the composition contains about 93 to 99.5 weight percent polyester, about 0.25 to 4 weight percent chain extender, and about 0.25 to 3 weight percent polyoxyalkyleneamine. Most preferably the composition contains about 96 to 99 weight percent polyester, about 0.5 to 2 weight percent chain extender, and about 0.5 to 2 weight percent polyoxyalkyleneamine.

The polyoxyalkyleneamine (s) may be added directly to the polyester or may be added in the form of a thermoplastic concentrate or masterbatch by blending it in a suitable thermoplastic carrier. Suitable thermoplastic carriers are polyesters or polyamides or mixtures thereof. Polyamides include those synthesized from lactams, alpha-omega amino acids, and diacid and diamine pairs. Such polyamides include, but are not limited to, polycaprolactam [polyamide 6], polyundecanolactam [polyamide 11], polyhexamethylene adipamide [polyamide 66], polylauryllactam [polyamide 12], poly (Hexamethylene dodecanediamide [polyamide 6, 12], poly (hexamethylene sebacamide) [polyamide 6, 10], poly (ethylene terephthalate), poly (butylene terephthalate), poly (trimethylene tere Phthalate) If polyoxyalkylenediamine is used in the masterbatch form, the amount of polyester in the formulation is controlled taking into account the amount of thermoplastic carrier in the polyoxyalkylenediamine masterbatch.

등록상표로 헌츠먼 코포레이션(Huntsman Corporation)으로부터 입수될 수 있다. 적당한 폴리옥시알킬렌디아민의 추가의 상세한 설명은 미국 특허 제3,654,370호에 기술되어 있다. Preferred polyoxyalkyleneamines are poly (oxyethylene) diamines (POED) having a molecular weight of about 2000. Another preferred polyoxyalkyleneamine that can be used in the invention is poly (oxypropylene) diamine, which also has a molecular weight of 2000. These compounds are known as Jeffamine

Trademarks may be obtained from Huntsman Corporation. Further details of suitable polyoxyalkylenediamines are described in US Pat. No. 3,654,370.

- 엑스텐드 1598은 스티렌 베이스 내에서 올리고머 다작용성 반응 물질의 20% 마스터배치이다. 이러한 마스터배치 형태에 대한 추가의 상세한 설명은 또한 블라시우스 등의 미국 특허 출원 공보 제US2004/0147678 A1호에 기술되어 있다. 적당한 사슬 연장제의 또 다른 예는 일가모드(Irgamod) RA20과 같은 일가모드

등록상표로 시바 스페셜티 케미칼스 인코포레이티드(Ciba Speciality Chemicals, Inc)로부터 입수 가능한 것이다. 다른 가능한 사슬 연장제는 제한되는 것은 아니지만 피로멜리트산 이무수물, 페닐렌비스옥사졸린, 카르보닐 비스(1-카프로락탐), 비스페놀 A-디글리시딜 에테르 기재 디에폭시드, 테트라글리 시딜 디아미노디페닐 메탄 기재 테트라에폭시드를 포함한다.Chain extenders, also known as coupling agents, have two or more functional groups that can react with another compound such that two or more of the compounds are bonded together. In principle, any difunctional (or more functional group) compound can be used for chain extension or coupling. Examples of suitable chain extenders are polyfunctional reaction materials, further examples of which are epoxy functional styrene (meth) acrylic copolymers. Suitable multifunctional epoxy compounds are described in US Patent Application Publication No. US2004 / 0138381 A1 to Blasius et al. CESA commercially available from Clariant Corporation

Extent 1598 is a 20% masterbatch of oligomeric multifunctional reactants in styrene base. Further details on this masterbatch form are also described in US Patent Application Publication No. US2004 / 0147678 A1 to Blasius et al. Another example of a suitable chain extender is a monovalent mode such as Irgamod RA20.

Trademarks are available from Ciba Specialty Chemicals, Inc. Other possible chain extenders include but are not limited to pyromellitic dianhydride, phenylenebisoxazoline, carbonyl bis (1-caprolactam), bisphenol A-diglycidyl ether based diepoxides, tetraglycidyl diamino Diphenyl methane based tetraepoxide.

Chain extenders can be added to the composition in a number of different ways. Most preferably, the chain extender is preblended or melt blended with the polyoxyalkyleneamine or polyoxyalkyleneamine masterbatch prior to addition to the polyester. Alternatively, chain extenders can be added to the polyester as a concentrate or in the form of a masterbatch. The choice of carrier for the chain extender for the masterbatch depends on the chain extender functional group reactivity with the carrier resin and for the preparation of polyoxyalkyleneamine masterbatches in other types known to those skilled in the art of masterbatch preparation in polyolefin based resins. It is a range of similar carrier resins used for. In some cases, depending on the chemical and physical properties of the chain extender, it may be added directly to the polyester and polyoxyalkyleneamines in the fiber spinning extruder.

Polyesters include thermoplastic polyesters such as those synthesized from one or more diacids and one or more glycols. Such polyesters include but are not limited to poly (ethylene terephthalate), poly (butylene terephthalate), poly (propylene terephthalate), poly (ethylene naphthalate), poly (propylene naphthalate), poly (butylene naphthalate) ), Poly (cyclohexane dimethanol terephthalate) and poly (lactic acid), or mixtures thereof.

In addition to the polyesters, polyoxyalkyleneamines and chain extenders described above, the compositions used in the practice of the present invention may contain other components. These include, but are not limited to, colorants, antioxidants, UV stabilizers, ozone crackers, oilproofing agents, stainproofing agents, antistatic agents, flame retardants, antimicrobial agents, lubricants, melt viscosity and melt strength enhancers. , Solid state polymerization accelerators and processing aids.

Fibers made from the compositions can be melt spun using various methods resulting in different products for many end use applications. The fibers can be spun using standard spinning machines known to those skilled in the art, including slow and fast spinning processes. The range of denier (dpf) per filament can be produced depending on the ultimate end use that such fibers can make, for example, low dpf for textile use and high dpf for use in carpets. The cross-sectional shape of the fiber may also be a wide range of possible shapes, including round, delta, trilobal, tetralobal, grooved or irregular.

These fibrous products are generally well known for downstream processing on molten spun fibers, including crimping, bulking, twisting, and the like, to provide a variety of products such as apparel, yarn, fabrics, upholstery fabrics, carpets and other flooring materials. Suitable yarns can be produced for incorporation into the The fibers can be blended, entangled, twisted or otherwise mixed with other fiber types including, but not limited to, synthetic fibers such as polyester, polyolefins or acrylics, or natural fibers such as wool or cotton, and mixtures thereof. .

Invention Example

Example 1

-엑스텐드 1598 및 폴리에스테르 담체 내의 무기 및 유기 안료로 이루어진 5%의 연한 베이지색 마스터배치("호밀(Rye)")를 더 배합하였다. 수득한 배합물은 용융 압출기 섬유 방사 라인 상에서 방사 하고 에어 제트 텍스쳐하여 Y 또는 트리로브 단면의 60 필라멘트로 이루어진 벌크 연속 필라멘트(BCF) 1300 데니어 얀(1300/60Y)을 수득하였다. BCF 얀의 두 말단은 길보스(Gilbos)-타입 에어 트위스터 상에서 함께 에어 트위스트되어 명칭 2600/120Y BCF 얀 번들을 생성하였다. 이 얀은 다발화되어 26온스의 면 중량을 부여하는 1/10 게이지 터프터상에서 레벨 루프 구조의 카펫을 생성하였다. 다발은 안감된 라텍스이었다.15% by weight of POED was blended, stranded, pelletized and dried with nylon 6, RV = 2.8 in a vented twin screw extruder. POED masterbatch with PET, IV = 0.67, and 2% CESA at 10% level in a vented twin screw extruder

A further 5% pale beige masterbatch (“Rye”) consisting of inorganic and organic pigments in Ext 1598 and a polyester carrier was further formulated. The resulting blend was spun on a melt extruder fiber spinning line and air jet textured to yield a bulk continuous filament (BCF) 1300 denier yarn (1300 / 60Y) consisting of 60 filaments of Y or trilob cross section. The two ends of the BCF yarn were air twisted together on a Gilbos-type air twister to produce the nominal 2600 / 120Y BCF yarn bundle. This yarn was bundled to create a carpet of level loop structure on a 1/10 gauge tufter that gave 26 ounces of cotton weight. The bundle was lined latex.

Example 2

-엑스텐드 1598 및 5%의 호밀 색 마스터배치를 이축 압출기 내에서 용융 배합하였다. 수득한 배합물은 실시예1에서와 유사한 방식으로 가공되어 2600/120Y BCF 얀이 생성되었다. 카펫은 실시예1에서 기술된 것과 유사한 구조의 BCF얀으로부터 생성되었다. 2% CESA with PET, IV = 0.67

-Extended 1598 and 5% rye color masterbatch were melt blended in a twin screw extruder. The resulting formulation was processed in a similar manner as in Example 1 to yield 2600 / 120Y BCF yarns. The carpet was produced from BCF yarns of a structure similar to that described in Example 1.

Example 3

Comparative (not Inventive) The 2600 / 120Y BCF yarns were spun, air textured and air twisted in a similar manner as in Example 1 consisting of a 5% rye color masterbatch with the same IV = 0.67 PET. The color masterbatch and PET were premelt blended prior to melt spinning the yarn. The BCF yarns were bundled and lined to give a carpet having a structure similar to that described in Example 1.

Example 4

The 10% POED masterbatch described in Example 1 was blended with PET, IV = 0.67 and the 5% rye color masterbatch was melt blended in a twin screw extruder. The resulting formulation was processed in a similar manner as in Example 1 to yield 2600 / 120Y BCF yarns. The carpet was made from BCF yarns of a structure similar to that described in Example 1.

Carpets prepared in Examples 1-4 were ASTM E648-03 "Standard Test Method for Critical Radiant Flux of Floor-Covering Systems Using a Radiant Heat Energy Source. Was tested for flame retardancy according to The results are shown in Table 1 below. Critical radiant flux represents the level of radiant heat energy required to withstand flame propagation in a carpet once ignited. Higher critical radiation flow rates indicate that the carpet has greater flame retardancy.

 Example No. Critical radiant flow rate / Wcm ^-2  Example 1  0.53  Example 2  0.38  Example 3  0.32  Example 4  0.40

The flame retardancy test results of Examples 1-4 detailed in Table 1 show that when the incorporation of separate chain extenders and polyoxyalkyleneamines (Examples 2 and 4, respectively) is incorporated into the polyester polymer matrix, It shows a smaller improvement in flame retardancy than polyester (Example 3). It has surprisingly been found that the addition of both chain extenders and polyoxyalkyleneamines to the polyester matrix (Example 1) is significantly improved in flame retardancy over unmodified polyester (Example 3).

Example 5

The 10 parts POED masterbatch described in Example 1 was melt compounded with 2 parts Irgamod RA20. The resulting formulation was added to PET, IV = 0.67 directly on the fiber spinning line at a 12% level and air jet textured to yield 1300 / 60Y BCF natural yarns. The two ends of the resulting yarns were air twisted together and the twisted yarns were bundled and latex lining into a level loop carpet structure having a yarn cotton weight of 20 oz.

Example 6

The second POED masterbatch / Ilgamod RA20 was formulated in a similar manner as in Example 5 with the ratio of 5 parts POED masterbatch to 2 parts monomodal RA20. The resulting formulation was added to PET, IV = 0.67 directly on the fiber spinning line at a rate of 7% and air jet textured to produce 1300 / 60Y BCF natural yarns. The two ends of the resulting yarns were air twisted together and the twisted yarns were bundled and latex lining into a level loop carpet structure having a yarn cotton weight of 20 oz.

Example 7

Natural yarns (no additives included) were spun and air textured from PET resin, IV = 0.67 to produce 1300 / 60Y BCF yarns. The two ends of the BCF yarns were air twisted together and the twisted yarns were bundled and latex lining into a level loop carpet structure having a yarn cotton weight of 20 oz.

The carpets prepared in Examples 5-7 were flame retardant in accordance with ASTM E648-03. Exemplary copy threshold flow rate of the Examples 5 and 6 were respectively 0.51Wcm ^-2 and 0.49Wcm ^-2. The critical radiation flow rate of Example 7 was 0.33 Wcm ^{- 2} . Both inventive compositions (Examples 5 and 6) exhibited improved flame retardancy than Control Example 7.

The above-described embodiments exist to demonstrate the advantages of the present invention. The specific techniques, conditions, materials, properties and reported data described to explain the nature of the invention are representative and should not be inferred as limiting the scope of the invention.

Example 8

-엑스텐드 1598 및 87.4부의 폴리프로필렌 테레프탈레이트 수지, IV=0.90과 배합하였다. 수득한 배합물은 방사하고 에어 제트 텍스쳐하여 1300/60Y BCF 얀을 수득하였다. BCF 얀의 두 말단은 함께 에어 트위스트 되고 트위스트된 얀은 20온스의 얀 면 중량을 갖는 레벨 루프 카펫 구조로 다발화 되었으며 라텍스 안감되었다. 10 parts POED masterbatch described in Example 1 0.6 parts 50% titanium dioxide masterbatch, 2 parts CESA on a vented twin screw extruder

-Blended with Extend 1598 and 87.4 parts polypropylene terephthalate resin, IV = 0.90. The resulting formulation was spun and air jet textured to yield 1300 / 60Y BCF yarns. The two ends of the BCF yarns were air twisted together and the twisted yarns were bundled into a level loop carpet structure with a 20 oz yarn cotton weight and latex lining.

Example 9

0.6 parts 50% titanium dioxide masterbatch and 99.4 parts polypropylene terephthalate resin, IV = 0.90 were combined, spun and air jet textured to yield 1300 / 60Y BCF yarn. The two ends of the BCF yarns were air twisted together and the twisted yarns were bundled into a level loop carpet structure with a 20 oz yarn cotton weight and latex lining.

Examples 8 and 9 were tested for flame retardancy according to ASTM E648-03. Example 8 0.33 Wcm ^- has a critical flow rate of ² copies. (Control) Example 9 Samples are given a critical radiant flux of 0.19 Wcm ⁻² . As in the foregoing examples, the inventive compositions (Example 8) showed significantly improved flame retardancy than the non-inventive (Example 9) comparative samples.

The above-described embodiments exist to demonstrate the advantages of the present invention. The specific techniques, conditions, materials, properties and reported data described to explain the nature of the invention are representative and should not be inferred as limiting the scope of the invention.

Claims (17)

Flame retardant compositions comprising: (a) thermoplastic polyester, (b) poly (oxyalkylene) diamines, and (c) chain extenders. The method of claim 1, Flame retardant composition, characterized in that the thermoplastic polyester is a fiber molded thermoplastic polyester. The method of claim 1, The thermoplastic polyester is poly (ethylene terephthalate), poly (butylene terephthalate), poly (propylene terephthalate), poly (ethylene naphthalate), poly (propylene naphthalate), poly (butylene naphthalate), poly (Cyclohexane dimethanol terephthalate) and poly (lactic acid), and a mixture selected from the group consisting of a flame retardant composition characterized in that it comprises a polyester. The method of claim 1, Flame retardant composition, characterized in that the poly (oxyalkylene) diamine comprises a compound selected from the group consisting of poly (oxyethylene) diamine and poly (oxypropylene) diamine, and mixtures thereof. The method of claim 1, Flame retardant composition, characterized in that the chain extender is a multifunctional reaction material. The method of claim 5, Flame retardant composition, characterized in that the multifunctional reactant is an epoxy functional styrene (meth) acrylic copolymer. The method of claim 5, The multifunctional reactants include pyromellitic dianhydride, phenylenebisoxazoline, carbonyl bis (1-caprolactam), bisphenol A-diglycidyl ether based diepoxide, tetraglycidyl diaminodiphenyl A flame retardant composition comprising a compound selected from the group consisting of methane based tetraepoxides and mixtures thereof. The method of claim 1, A flame retardant composition comprising from 93 to 99.5 weight percent polyester, from 0.25 to 4 weight percent chain extender, and from 0.25 to 3 weight percent poly (oxyalkylene) diamine. 9. The method of claim 8, A flame retardant composition comprising 96 to 99 wt% polyester, 0.5 to 2 wt% chain extender, and 0.5 to 2 wt% poly (oxyalkylene) diamine. Flame retardant compositions comprising: (a) thermoplastic polyester, (b) a concentrate comprising both polyoxyalkylenediamine and a carrier resin, wherein the carrier resin comprises a thermoplastic polyamide or thermoplastic polyester, and (c) chain extenders. The method of claim 10, Flame retardant composition, characterized in that the thermoplastic polyester is a fiber molded thermoplastic polyester. The method of claim 10, The thermoplastic polyester is poly (ethylene terephthalate), poly (butylene terephthalate), poly (propylene terephthalate), poly (ethylene naphthalate), poly (propylene naphthalate), poly (butylene naphthalate), poly (Cyclohexane dimethanol terephthalate) and poly (lactic acid), and a mixture selected from the group consisting of a flame retardant composition characterized in that it comprises a polyester. The method of claim 10, Flame retardant composition, characterized in that the poly (oxyalkylene) diamine comprises a compound selected from the group consisting of poly (oxyethylene) diamine and poly (oxypropylene) diamine, and mixtures thereof. The method of claim 10, Flame retardant composition, characterized in that the chain extender is a multifunctional reaction material. The method of claim 14, Flame retardant composition, characterized in that the multifunctional reactant is an epoxy functional styrene (meth) acrylic copolymer. The method of claim 14, The multifunctional reactants are pyromellitic dianhydride, phenylenebisoxazoline, carbonyl bis (1-caprolactam), bisphenol A-diglycidyl ether based diepoxide, tetraglycidyl diaminodiphenyl methane A flame retardant composition comprising a compound selected from the group consisting of a base tetraepoxide, and mixtures thereof. The method of claim 10, The carrier resin is polyamide 6, polyamide 11, polyamide 66, polyamide 12, polyamide 6,12, polyamide 6,10, poly (ethylene terephthalate), poly (butylene terephthalate), poly (tree Methylene terephthalate), and mixtures thereof.