TWI758792B - Fiber masterbatch and melting spinning fiber - Google Patents

Abstract

A fiber masterbatch including a polyetherimide, a polyethylene terephthalate, and a polyimide is provided. A glass transition temperature of the polyimide is between 140^o C and 170^o C, a 10% thermogravimetric loss temperature of the polyimide is between 500^o C and 550^o C, and when the polyimide is dissolved in N-methyl-2-pyrrolidone and a solid content of the polyimide is 15 wt%, a viscosity of the polyimide is between 80 cP and 230 cP. A melting spinnindg fiber obtained by using the fiber masterbatch is also provided.

Description

Fiber Masterbatch and Melt Spinning Fiber

The present invention relates to a textile material, and more particularly, to a fiber masterbatch for melt spinning and melt spun fibers made therefrom.

Many thermoplastic resins called "engineering plastics" have been widely used in various fields due to their excellent properties such as heat resistance, chemical resistance, and flame retardancy. However, there are still limitations in the use of engineering plastics. For example, the processing temperature of polyetherimide is quite high (between 350°C and 380°C), which is not easy to achieve for general machines. In addition, when polyvinylidene fluoride is molded at high temperature, if the processing temperature exceeds 320°C, hydrofluoric acid, which is highly corrosive, is easily generated. Therefore, how to improve the applicability of engineering plastics is still an important topic of active research.

The invention provides a fiber masterbatch, which has good thermal processability, suitable thermal processing temperature, good flexibility, good flame retardancy and good heat resistance, does not produce droplet phenomenon after burning, and is suitable for use in textiles.

The invention provides a melt-spun fiber, which has good softness, good flame retardancy, good heat resistance and low process temperature, and does not produce droplet phenomenon after burning.

The fiber masterbatch of the present invention includes polyetherimide (PEI), polyethylene terephthalate (PET) and polyimide, wherein the glass transition temperature of polyimide is between 140 ^o C to 170 ^o C, 10% TGA loss temperature for polyimide between 500 ^o C and 550 ^o C, and when polyimide is dissolved in N-methyl-2-pyrrolidone And at 15 wt% solids, the viscosity ranged from 80 cP to 230 cP.

The melt-spun fibers of the present invention are made by using the fiber masterbatch as described above.

Based on the above, the fiber masterbatch of the present invention comprises polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^° C to about 170 ^° C, and 10% thermogravimetric loss temperature between A polyimide having a viscosity between about 80 cP and about 230 cP when dissolved in NMP at 15 wt% solids between about 500 ^o C and about 550 ^o C, whereby the fibrous masterbatch can have Good thermal processability, appropriate thermal processing temperature, good flexibility, good heat resistance and good flame retardancy, no melting drop after burning, and suitable for use in textiles. On the other hand, the melt-spun fiber of the present invention is produced from the aforementioned fiber masterbatch, whereby the melt-spun fiber can have good flexibility, good heat resistance, good flame retardancy and low process temperature, and will not produce melted droplets after burning Phenomenon.

In order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following specific embodiments are described in detail as follows.

As used herein, a range represented by "one value to another value" is a general representation that avoids listing all the values in the range in the specification. Therefore, the recitation of a specific numerical range includes any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were expressly written in the specification. same range.

In this document, the structure of a polymer or group is sometimes represented by a skeleton formula. This notation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, where atoms or atomic groups are clearly drawn in the structural formula, the drawing shall prevail.

As used herein, "about," "approximately," "substantially," or "substantially" includes the stated value and the average within an acceptable deviation of the particular value as determined by one of ordinary skill in the art, taking into account all The measurement in question and the specific amount of measurement-related error (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or within ±30%, ±20%, ±15%, ±10%, ±5%, for example. Furthermore, the terms "about", "approximately", "substantially", or "substantially" as used herein may be used to select a more acceptable range of deviation or standard deviation depending on the nature of the measurement or other properties, rather than a standard Deviations apply to all properties.

In order to provide a fiber masterbatch that has good thermal processability, appropriate thermal processing temperature, good flexibility and good flame retardancy, does not produce droplets after burning, and is suitable for making melt-spun fibers, the present invention provides a fiber masterbatch, It achieves the above-mentioned advantages. Hereinafter, the embodiment is given as an example by which the present invention can be actually implemented.

The fiber masterbatch proposed by an embodiment of the present invention includes polyetherimide (PEI), polyethylene terephthalate (PET) and polyimide (PI). Hereinafter, each of the above-mentioned components will be described in detail.

式I。也就是說，聚醚醯亞胺可由雙酚A型二醚二酐（4,4’-(4,4’-isopropylidenediphenoxy)bis(phthalic anhydride)，簡稱BPADA）與間苯二胺（m-phenylenediamine，簡稱m-PDA）進行反應而得。另外，在本實施方式中，聚醚醯亞胺亦可為市售品或經回收的粉體（亦即，二次料），其中所述市售品例如是：由沙特基礎工業公司（Sabic）製造的紡絲級的ULTEM 9011 PEI、ULTEM 1010 PEI。在聚醚醯亞胺為二次料時，可具有降低成本的優勢。在本實施方式中，聚醚醯亞胺的重量平均分子量(Mw)可介於約44000 g/mol至約50000 g/mol之間。另外，聚醚醯亞胺本身燃燒後不會產生融滴現象且具有良好的耐熱性及可染性，故包括聚醚醯亞胺的纖維母粒可具有燃燒後不會產生融滴現象、良好耐熱性及良好可染性等性質。Polyetherimide is a thermoplastic amorphous polymer with solvent-soluble properties. In this embodiment, the polyetherimide may include repeating units represented by the following formula I:

Formula I. That is to say, polyetherimide can be obtained from bisphenol A-type diether dianhydride (4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), referred to as BPADA) and m-phenylenediamine (m-phenylenediamine). , referred to as m-PDA) for the reaction. In addition, in this embodiment, the polyetherimide can also be a commercial product or a recovered powder (that is, a secondary material), wherein the commercial product is, for example, produced by Saudi Basic Industries Corporation (Sabic ) of spinning grade ULTEM 9011 PEI, ULTEM 1010 PEI. When polyetherimide is the secondary material, it can have the advantage of reducing cost. In this embodiment, the weight average molecular weight (Mw) of the polyetherimide may be between about 44,000 g/mol and about 50,000 g/mol. In addition, polyetherimide itself will not produce droplet phenomenon after burning and has good heat resistance and dyeability, so the fiber masterbatch including polyetherimide can have no droplet phenomenon after burning, good Heat resistance and good dyeability properties.

In this embodiment, polyethylene terephthalate can be a commercial product or a recycled powder (ie, a secondary material), wherein the commercial product is, for example, a product manufactured by Shinko Synthetic Fiber Company (SHINKONG PET U25961 from NANYA PLASTIC CO., or PET 3802 from NANYA PLASTIC CO. When polyethylene terephthalate is the secondary material, it can have the advantage of reducing cost. In this embodiment, the weight average molecular weight (Mw) of the polyethylene terephthalate may be between about 20,000 g/mol to about 30,000 g/mol.

In this embodiment, the glass transition temperature of the polyimide is between about 140 ^° C and about 170 ^° C, and the 10% thermogravimetric loss temperature of the polyimide is between about 500 ^° C and about 550 ^° C. , and when the polyimide was dissolved in NMP and the solids content was about 15 wt%, the viscosity was between about 80 cP and about 230 cP. If the glass transition temperature, 10% thermogravimetric loss temperature and viscosity of the polyimide do not fall within the aforementioned ranges, the thermal processability and thermal stability of the fiber masterbatch are not good.

式1， 其中Ar為衍生自含有芳香族基的四羧酸二酐化合物的四價有機基，A為衍生自含有芳香族基的二胺化合物的二價有機基。也就是說，Ar為含有芳香族基的四羧酸二酐化合物中除了2個羧酸酐基（-(CO)₂ O）以外的殘基；而A為含有芳香族基的二胺化合物中除了2個氨基（-NH₂ ）以外的殘基。在本實施方式中，所述四價有機基和所述二價有機基中的至少一者含有醚基。也就是說，所述含有芳香族基的四羧酸二酐化合物和所述含有芳香族基的二胺化合物中的至少一者含有醚基。在本文中，所述含有芳香族基的四羧酸二酐化合物亦稱為二酐單體，而所述含有芳香族基的二胺化合物亦稱為二胺單體。在本實施方式中，聚醯亞胺可透過二酐單體與二胺單體進行反應而得。In this embodiment, the polyimide is an ether group-containing polyimide, whereby the thermal processability of the fiber masterbatch can be improved. In this embodiment, the polyimide may include repeating units represented by Formula 1:

Formula 1, wherein Ar is a tetravalent organic group derived from an aromatic group-containing tetracarboxylic dianhydride compound, and A is a divalent organic group derived from an aromatic group-containing diamine compound. That is to say, Ar is the residue except for two carboxylic acid anhydride groups (-(CO) ₂ O) in the tetracarboxylic dianhydride compound containing an aromatic group; and A is the residue in the diamine compound containing an aromatic group, except Residues other than 2 amino groups (-NH ₂ ). In this embodiment, at least one of the tetravalent organic group and the divalent organic group contains an ether group. That is, at least one of the aromatic group-containing tetracarboxylic dianhydride compound and the aromatic group-containing diamine compound contains an ether group. Herein, the aromatic group-containing tetracarboxylic dianhydride compound is also referred to as a dianhydride monomer, and the aromatic group-containing diamine compound is also referred to as a diamine monomer. In this embodiment, the polyimide can be obtained by reacting a dianhydride monomer with a diamine monomer.

、

、

、

或

。具體而言，用來製備聚醯亞胺的二酐單體可為雙酚A型二醚二酐（4,4’-(4,4’-isopropylidenediphenoxy)bis(phthalic anhydride)，簡稱BPADA）、二苯醚四甲酸二酐（oxydiphthalic anhydride)，簡稱ODPA）、均苯四甲酸酐（pyromellitic dianhydride，簡稱PMDA）、3,3’,4,4’-二苯酮四酸二酐（3,3’,4,4’-benzophenonetetracarboxylic dianhydride，簡稱BTDA）、或3,3’,4,4’-聯苯四羧酸二酐（3,3’,4,4’-biphenyltetracarboxylic dianhydride，簡稱BPDA）。In this embodiment, Ar can be

,

,

,

or

. Specifically, the dianhydride monomer used to prepare the polyimide can be bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), BPADA for short), Oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (3,3 ',4,4'-benzophenonetetracarboxylic dianhydride, referred to as BTDA), or 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride, referred to as BPDA).

、

、

、

、

、

、

或

。具體而言，用來製備聚醯亞胺的二胺單體可為間苯二胺（meta-phenylene diamine，簡稱m-PDA）、2,2-雙[(4-氨基苯氧基)苯基]丙烷（簡稱BAPP）、4,4’-二氨基二苯基碸（4,4’-diaminodiphenyl sulfone）、4,4’-二氨基二苯基醚（4,4’-oxydianiline/4,4’-diaminodiphenyl ether，簡稱ODA）、3,3’-二胺基二苯甲酮（3,3’-diaminobenzophenone）、1,3-二(4-氨苯氧基)苯（1,3-bis(4-aminophenoxy) benzene，簡稱TPE-R）、3,4’-二氨基二苯基醚（3,4’-oxydianiline/3,4’-diaminodiphenyl ether）或3,5-二氨基苯甲酸（3,5-diaminobenzoic acid，簡稱DABA）。In this embodiment, A can be

,

,

,

,

,

,

or

. Specifically, the diamine monomer used to prepare the polyimide can be meta-phenylene diamine (m-PDA for short), 2,2-bis[(4-aminophenoxy)phenyl ] Propane (BAPP for short), 4,4'-diaminodiphenyl sulfone (4,4'-diaminodiphenyl sulfone), 4,4'-diaminodiphenyl ether (4,4'-oxydianiline/4,4 '-diaminodiphenyl ether, referred to as ODA), 3,3'-diaminobenzophenone (3,3'-diaminobenzophenone), 1,3-bis(4-aminophenoxy)benzene (1,3-bis (4-aminophenoxy) benzene, referred to as TPE-R), 3,4'-diaminodiphenyl ether (3,4'-oxydianiline/3,4'-diaminodiphenyl ether) or 3,5-diaminobenzoic acid ( 3,5-diaminobenzoic acid, referred to as DABA).

Specifically, in this embodiment, the polyimide can be prepared by, for example, a condensation polymerization method and a thermal cyclization method, or a condensation polymerization method and a chemical cyclization method. The condensation polymerization method, the thermal cyclization method, and the chemical cyclization method, respectively, can be carried out using any procedure known to those of ordinary skill in the art. In one embodiment, the preparation of polyimide by condensation polymerization and chemical cyclization may include the following steps: performing condensation polymerization of dianhydride monomer and diamine monomer in a solvent to form a polyimide solution Then, the dehydrating agent and the imidizing agent are added into the polyimide solution to carry out the imidization reaction (ie, the dehydration cyclization reaction) to form the polyimide. In another embodiment, the preparation of polyimide by condensation polymerization and thermal cyclization may include the following steps: subjecting dianhydride monomers and diamine monomers to condensation polymerization in a solvent to form polyamides After the solution, the polyimide solution is heated to carry out an imidization reaction (ie, a dehydration cyclization reaction) to form a polyimide.

The solvent is not particularly limited as long as it can dissolve the dianhydride monomer and the diamine monomer. Specifically, examples of the solvent include (but are not limited to): N,N-dimethylacetamide (N,N-dimethylacetamide; DMAc), N,N-dimethylformamide (N,N-dimethylacetamide) -dimethylformamide; DMF), N,N'-diethylacetamide, NMP, γ-butyrolactone, triamide hexamethylphosphate and other amide solvents; tetramethylurea, N,N-dimethylformamide Urea-based solvents such as ethyl urea; sulfite or sulfite-based solvents such as dimethyl sulfoxide, diphenyl sulfite, and tetramethyl sulfite; halogenated alkyl-based solvents such as chloroform and methylene chloride; aromatics such as benzene and toluene Hydrocarbon-based solvents; phenol-based solvents such as phenol and cresol; or ether-based solvents such as tetrahydrofuran, 1,3-dioxolane, dimethyl ether, diethyl ether, and p-cresol methyl ether. The above-mentioned solvents may be used alone or in combination of two or more. In order to improve the solubility and reactivity of the dianhydride monomer and the diamine monomer, the solvent is preferably an amide-based solvent such as DMAc, DMF, and NMP. In addition, examples of the dehydrating agent include (but are not limited to): acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride or trifluoroacetic anhydride; examples of the imidizing agent include, but are not limited to: pyridine, picoline, quinoline or isoquinoline.

In addition, in this embodiment, the number of types of diamine monomers and the number of types of dianhydride monomers used to prepare polyimide are not limited, as long as the glass transition temperature of the prepared polyimide is between Between about 140 ^o C and about 170 ^o C, 10% thermogravimetric loss temperature between about 500 ^o C and about 550 ^o C, and viscosity in the case where the solvent is NMP and 15 wt% solids Between 80 cP and 230 cP with suitable hot-melt processability and solvent-soluble properties. For example, polyimides can be obtained by reacting a diamine monomer with a dianhydride monomer. As another example, polyimide can be obtained by reacting multiple diamine monomers with one dianhydride monomer, one diamine monomer with multiple dianhydride monomers, or multiple diamine monomers with multiple dianhydride monomers. Dianhydride monomer reaction derived.

In this embodiment, the manufacturing method of the fiber masterbatch may include: sequentially performing a mixing and dispersing process and a kneading and granulating process on the polyetherimide, polyethylene terephthalate and polyimide. In one embodiment, the mixing and dispersing process is performed at room temperature, for example, and the process temperature used in the kneading and granulation process is, for example, between about 310 ^° C to about 330 ^° C.

In some embodiments, in the fiber masterbatch, the content of polyetherimide is greater than or equal to about 25 parts by weight and less than or equal to about 80 parts by weight, and the content of polyethylene terephthalate is greater than or equal to About 20 parts by weight and less than or equal to about 70 parts by weight and the content of the polyimide is about 1 part by weight to about 5 parts by weight. If the amount of polyetherimide used is less than about 25 parts by weight, the heat resistance and flame retardancy of the fiber masterbatch are not good, and the phenomenon of melting droplets is likely to occur; if the amount of polyetherimide used is more than 80 parts by weight If the amount is too high, the thermal processability of the fiber masterbatch is not good, and if the thermal processing temperature is too high, it is difficult to produce melt-spun fibers. Conversely, if the amount of polyethylene terephthalate used is less than about 20 parts by weight, the thermal processability of the fiber masterbatch is not good; if the amount of polyethylene terephthalate used is higher than about 70 parts by weight , the heat resistance and flame retardancy of the fiber masterbatch are not good. If the amount of polyimide used is less than about 1 part by weight or more than 5 parts by weight, it is difficult to make polyetherimide and polyethylene terephthalate compatible, and it is difficult to produce fiber masterbatches.

Additionally, in some embodiments, the fiber masterbatch has a melt index (MI) of about 70 g/10min to about 150 g/10min at about 320 ^° C. Generally, the processing temperature of polyetherimide is between 350°C and 380°C. In view of this, including polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^° C to about 170 ^° C, 10% thermogravimetric loss temperature between about 500 ^° C to about 170 ° C Fiber masterbatches of polyimide with viscosity between about 80 cP to about 230 cP when dissolved in NMP and 15 wt% solids between about 550 ^o C have good thermal processability and reduced hot working temperature.

Additionally, in some embodiments, the fibrous masterbatch has a glass transition temperature (Tg) between about 100 ^° C and about 170 ^° C. In comparison, typical polyetherimides have a glass transition temperature of about 214°C. Thus, including polyetherimide, polyethylene terephthalate, and glass transition temperatures ranging from about 140 ^° C to about 170 ^° C, 10% thermogravimetric loss temperatures ranging from about 500 ^° C to about 550°C ^o C, fibrous masterbatches of polyimide with viscosity between about 80 cP to about 230 cP when dissolved in NMP and 15 wt% solids content have good softness. It is worth mentioning that the fiber masterbatch is a material with good softness, so the fiber masterbatch can be applied to textiles, and when applied to textiles, the fiber masterbatch can be processed into fibers or films, etc. form exists.

In addition, within the scope of not impairing the essential effect of the fiber masterbatch, the fiber masterbatch can be blended with additives as required, so as to further increase the applicability and commercial value of the fiber masterbatch. The additives include, for example, flame retardants, antistatic agents, antibacterial agents, colorants or combinations thereof.

It is worth noting that, in this embodiment, the fiber masterbatch includes polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^o C to about 170 ^o C, 10% heat A polyimide having a weight loss temperature between about 500 ^° C and about 550 ^° C and a viscosity between about 80 cP and about 230 cP when dissolved in NMP and having a solids content of 15 wt%, whereby The fiber masterbatch can have good thermal processability, appropriate thermal processing temperature, good flexibility, good heat resistance and good flame retardancy, and will not produce droplets after burning, and is suitable for use in textiles. In addition, because the fiber masterbatch can have good flexibility, good heat resistance and good flame retardancy, and will not produce droplets after burning, the fiber masterbatch can be less prone to problems such as embrittlement or breakage after high temperature treatment. In this way, the application and commercial value of the fiber masterbatch and the fibers obtained by using it in the textile industry have been greatly improved, such as the manufacture of fire-fighting clothing, heat-insulating gloves, Textiles such as fire blankets.

In addition, as described above, the fiber masterbatch of the present invention can exist in the form of fibers, films, or the like. Hereinafter, the fiber masterbatch will be used as an example to illustrate the fiber type.

Another embodiment of the present invention provides a melt-spun fiber made using the fiber masterbatch of any of the preceding embodiments. That is, the melt-spun fibers are made of polyetherimide, polyethylene terephthalate, and glass transition temperatures ranging from about 140 ^° C to about 170 ^° C, and 10% thermogravimetric loss temperatures ranging from A polyimide having a viscosity between about 80 cP and about 230 cP when dissolved in NMP at 15 wt% solids between about 500 ^° C and about 550 ^° C.

In some embodiments, the melt-spun fibers are pre-oriented yarns (POY; also known as semi-extended yarns). In an embodiment in which the melt-spun fibers are pre-oriented fibers, the preparation method of the melt-spun fibers includes, for example: after drying the fiber masterbatch to remove moisture, the dried fiber masterbatch is subjected to a melt-spinning process, wherein drying The temperature of the fiber masterbatch is, for example, between about 120 ^° C and about 140 ^° C, the time for drying the fiber masterbatch is, for example, more than about 12 hours, and the melt spinning temperature is, for example, between about 320 ^° C and about 350 ^° C Between C, the take-up speed is, for example, between about 700 m/min and about 1000 m/min.

In other embodiments, the melt-spun fibers are fully oriented yarns (FOY). In an embodiment in which the melt-spun fibers are fully extended fibers, the preparation method of the melt-spun fibers includes, for example, the following steps. First, referring to the above method, the fiber masterbatch is subjected to a melt spinning process to form a pre-oriented yarn (semi-drawn yarn). Next, the above-mentioned pre-oriented yarn (semi-stretched yarn) is subjected to a thermal stretching process using, for example, a thermal roll stretching machine or a thermal stretching braiding machine, wherein the thermal stretching temperature is, for example, between about 70 ^o C and about 120 ^o C, and the heat The elongation ratio is, for example, between about 20% and about 60%.

As previously described, in this embodiment, the melt spinning temperature of the melt spun fibers may be between about 320 ^° C to about 350 ^° C. Generally, the melt spinning temperature of the polyetherimide is greater than about 380°C. In view of this, melt-spun fibers made using the fiber masterbatches of any of the foregoing embodiments can be produced at reduced melt-spinning temperatures with good applicability. In other words, the fiber masterbatch has good hot workability and reduced hot working temperature.

In this embodiment, the fiber fineness of the melt-spun fibers may be between about 50d/96f and about 220d/48f. That is, in this embodiment, the fiber masterbatches of any of the preceding embodiments can be used to produce melt-spun fibers having a fiber gauge of between about 0.5 dpf and about 4.6 dpf. In other words, the melt-spun fibers may have a Denier per Filament (D.P.F.) of about 0.5 to about 4.6.

In some embodiments, when the meltspun fibers are pre-oriented filaments, the fiber strength is greater than or equal to about 1.5 g/d. In other embodiments, when the melt-spun fibers are pre-oriented filaments, the fiber elongation is greater than or equal to about 45%. In yet other embodiments, when the melt-spun fibers are fully drawn filaments with a draw ratio of 55%, the fiber strength is greater than or equal to about 3 g/d and the fiber elongation is greater than or equal to about 35%. That is, meltspun fibers made using the fiber masterbatches of any of the preceding embodiments may have good mechanical properties suitable for preparation into textiles.

It is worth noting that, in this embodiment, the melt-spun fibers are composed of polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^o C to about 170 ^o C, 10% Fibers of polyimide having a thermogravimetric loss temperature between about 500 ^° C and about 550 ^° C and a viscosity between about 80 cP and about 230 cP when dissolved in NMP and having a solids content of 15 wt% The masterbatch is prepared, whereby the melt-spun fibers can have low process temperature, good flexibility, good flame retardancy and good heat resistance, and will not produce droplets after burning.

Hereinafter, the features of the present invention will be described more specifically with reference to Examples 1 to 14 and Comparative Examples 1 to 3. Although the following examples are described, the materials used, their amounts and ratios, processing details, processing flow, and the like may be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be construed restrictively by the embodiments described below. Synthesis Example 1-2

After the polyimide of Synthesis Example 1-2 was formed according to the preparation method of the polyimide disclosed above, the polyimide of Synthesis Example 1-2 was subjected to glass transition temperature (Tg), 10% thermogravimetric Measurement of loss temperature (T _d10% ) and viscosity. The descriptions of the aforementioned measurement items are as follows, and the measurement results are shown in Table 1. < Measurement of glass transition temperature (Tg)>

Using a thermomechanical analyzer (made by Maia, model: DSC200 F3), the polyimide of Synthesis Example 1-2 was respectively subjected to glass transfer under the conditions of nitrogen atmosphere and heating rate set to 10 ^o C/min Determination of temperature ( ^o C). <Measurement of 10% thermogravimetric loss temperature (T _d10% )>

Using a thermogravimetric analyzer (manufactured by TA Instruments, model: Q50), the polyimide of Synthesis Example 1-2 was measured and recorded in a nitrogen atmosphere and a heating rate set to 20 ^o C/min. The weight change of polyimide, wherein the temperature measured when each polyimide loses 10% by weight is the 10% thermogravimetric loss temperature ( ^° C). < Measurement of viscosity>

First, the polyimides of Synthesis Examples 1-2 were respectively dissolved in a solvent NMP to form a plurality of sample solutions having a solid content of 15 wt %. Next, the sample solutions were respectively subjected to viscosity (cP) measurement at room temperature by a rotary viscometer (manufactured by Brookfield, USA, model: DV-II+ Pro Viscometer).

Table 1 Tg( ^oC ) T _d10% ( ^o C) Viscosity (cP) Synthesis Example 1 141 509 81 Synthesis Example 2 168 549 228 Example 1

The fiber masterbatch of Example 1 was prepared by the following steps. 27 parts by weight of polyetherimide (ULTEM 1010 PEI manufactured by Sabic), 70 parts by weight of polyethylene terephthalate (PET 3802 manufactured by Nan Ya Plastics Corporation) and 3 parts by weight The polyimide of Synthesis Example 1 was added to a high-speed mixer (manufactured by Qiaolong Machinery Co., Ltd., model FC-25) for a mixing and dispersing process for 3 minutes to form a powder composition. Next, the powder composition was added to a twin-screw extruder, and the kneading and granulation process was carried out under the conditions of a temperature of 340 ^° C and a rotation speed of 850 rpm, so as to obtain the fiber masterbatch of Example 1. Example 2 to Example 8

The fiber masterbatches of Examples 2 to 8 were prepared in the same steps as those of Example 1, and the differences were: the type of polyimide used, and/or polyetherimide, polyterephthalate The amount of ethylene formate and polyimide used (as shown in Table 2).

Table 2 The amount of polyetherimide used The amount of polyethylene terephthalate used Polyimide type Usage amount Example 1 27 parts by weight 70 parts by weight Synthesis Example 1 3 parts by weight Example 2 36 parts by weight 60 parts by weight Synthesis Example 1 4 parts by weight Example 3 70 parts by weight 30 parts by weight Synthesis Example 1 1 part by weight Example 4 80 parts by weight 20 parts by weight Synthesis Example 1 1 part by weight Example 5 80 parts by weight 20 parts by weight Synthesis Example 1 1.5 parts by weight Example 6 80 parts by weight 20 parts by weight Synthesis Example 1 2 parts by weight Example 7 47.5 parts by weight 50 parts by weight Synthesis Example 2 2.5 parts by weight Example 8 66.5 parts by weight 30 parts by weight Synthesis Example 2 3.5 parts by weight Comparative Example 1

In Comparative Example 1, other polymers were not mixed with polyetherimide (ULTEM 1010 PEI manufactured by Sabic). That is, in Comparative Example 1, granulation was carried out using the commercially available polyetherimide ULTEM 1010 PEI as it is. Comparative Example 2

In Comparative Example 2, other polymers were not mixed with polyethylene terephthalate (PET 3802 manufactured by Nan Ya Plastic Co., Ltd.). That is, in Comparative Example 2, PET 3802, a commercially available polyethylene terephthalate, was directly used for granulation. Comparative Example 3

The fiber masterbatch of Comparative Example 3 was prepared by the following procedure. 40 parts by weight of polyetherimide (ULTEM 1010 PEI manufactured by Sabic) and 60 parts by weight of polyethylene terephthalate (PET 3802 manufactured by Nan Ya Plastics Corporation) were added to high speed mixing The mixing and dispersing process was carried out for 3 minutes in a machine (manufactured by Qiaolong Machinery Co., Ltd., model FC-25) to form a powder composition. Next, the powder composition was added to a twin-screw extruder, and the kneading and granulation process was carried out under the conditions of a temperature of 340 ^° C and a rotation speed of 850 rpm to obtain the fiber masterbatch of Comparative Example 3. That is, in Comparative Example 3, no polyimide was used.

After that, the fiber masterbatches of Examples 1-8, the fiber masterbatches of Comparative Example 1 (ie, ULTEM 1010 PEI), the fiber masterbatches of Comparative Example 2 (ie, PET 3802) and the fiber masterbatches of Comparative Example 3 were respectively subjected to glass processing. Measurement of transition temperature (Tg), cold crystallization temperature (Tc), melting point (Tm) and melt index (MI), and evaluated the fiber masterbatch of Examples 1-8, the fiber masterbatch of Comparative Example 1 (ie, ULTEM 1010 PEI), the fiber masterbatch of Comparative Example 2 (ie, PET 3802) and the fiber masterbatch of Comparative Example 3, the crystallization state, surface morphology and melting drop phenomenon. The descriptions of the aforementioned items are as follows, and the measurement results and evaluation results are shown in Table 3. < Measurement of thermal properties>

The fiber masterbatches of Examples 1-8, the fiber masterbatches of Comparative Example 1 (ie, ULTEM 1010 PEI), the fiber masterbatches of Comparative Example 2 (ie, PET 3802) and the fiber masterbatches of Comparative Example 3 were respectively pressed into flakes. Next, using a thermomechanical analyzer (manufactured by Maia, model: DSC200 F3), these flakes were subjected to glass transition temperature ( ^{oC )} measurements in a nitrogen atmosphere and a heating rate set to 10oC/min, respectively. measurement. In addition, the melting point ( ^o C) and cold crystallization temperature ( ^o C) of each of the above are obtained from the above-mentioned heating curve and cooling curve. < Measurement of Melt Index (MI)>

According to the specification of ASTM D-1238, the fiber masterbatches of Examples 1-8, the fiber masterbatches of Comparative Example 1 (ie ULTEM 1010 PEI), the fiber masterbatches of Comparative Example 2 (ie PET 3802) and Comparative Example 3 were measured respectively. The melt index (g/10 min) of the fiber masterbatch, in which the weight load is 5 kg, and the test temperature varies according to the test sample used. Please refer to Table 2 for the detailed test temperature. In general, the higher the melt index, the better the hot workability and the better the thermal fluidity. ＜ Determination of crystal condition＞

Judging from the measurement results of the above thermal properties: the fiber masterbatch with a melting point means that it has polymer crystallization behavior. < Discrimination of Surface Type>

The appearance of the crystalline fiber masterbatch is opaque, and its surface morphology can be determined by this. ＜ Evaluation of the droplet phenomenon＞

The fiber masterbatches of Examples 1-8, the fiber masterbatches of Comparative Example 1 (ie, ULTEM 1010 PEI), the fiber masterbatches of Comparative Example 2 (ie, PET 3802) and the fiber masterbatches of Comparative Example 3 were respectively pressed into flakes. After the flakes were burnt, the presence or absence of dripping was observed with the naked eye, and the evaluation results are shown in Table 3 below.

table 3 Tg ( ^oC ) Tc ( ^oC ) Tm ( ^oC ) Crystalline status surface pattern Example 1 101 160 252 crystallization foggy Example 2 100 188 250 crystallization foggy Example 3 151 N/A N/A Amorphous Transparent Example 4 165 N/A N/A Amorphous Transparent Example 5 168 N/A N/A Amorphous Transparent Example 6 170 N/A N/A Amorphous Transparent Example 7 131 N/A 240 crystallization Transparent Example 8 156 N/A N/A Amorphous Transparent Comparative Example 1 214 N/A N/A Amorphous Transparent Comparative Example 2 80 N/A 251.8 crystallization foggy Comparative Example 3 94 N/A 253 crystallization semi-fog

Table 3 (continued) MI(g/10 min)/test temperature ( ^o C) Melted or not Example 1 191/300 no Example 2 148/300 no Example 3 146/320 no Example 4 74/320 no Example 5 77/320 no Example 6 78/320 no Example 7 195/300 no Example 8 51/300 no Comparative Example 1 13/340 no Comparative Example 2 511/300 Yes Comparative Example 3 N/A Yes

As can be seen from Table 3 above, compared to the ULTEM 1010 PEI of Comparative Example 1, the fiber masterbatches of Examples 1-8 had a reduced glass transition temperature. This result shows that the invention includes polyetherimide, polyethylene terephthalate and glass transition temperatures ranging from about 140 ^° C to about Between 170 ^o C, 10% TGA loss temperature between about 500 ^o C to about 550 ^o C, viscosity when dissolved in NMP at 15 wt% solids between about 80 cP to about 230 cP The polyimide fiber masterbatch has reduced glass transition temperature and good softness.

As can be seen from the above Table 3, compared with the melt index and hot working temperature of ULTEM 1010 PEI of Comparative Example 1, the fiber masterbatches of Examples 1-8 have good fluidity at lower hot working temperature. This result shows that the present invention includes polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^° C to about 170 ^° C, 10% TGR loss temperature is between about 500°C Fibrous masterbatches of polyimide with viscosity between about 80 cP and about 230 cP when dissolved in NMP and 15 wt% solids between ^o C and about 550 ^o C have good hot processability , good thermal fluidity and reduced thermal processing temperature.

As can be seen from the above Table 3, compared with the PET3802 of Comparative Example 2 and the fiber masterbatch without polyimide added in Comparative Example 3, the fiber masterbatches of Examples 1-8 and the ULTEM 1010 PEI of Comparative Example 1 burned Afterwards, it will not cause the phenomenon of melting and dripping. It is worth mentioning that the fiber masterbatch of Example 2 and the fiber masterbatch of Comparative Example 3 have similar proportions of polyetherimide and polyethylene terephthalate, but the fiber masterbatch of Example 2 is burning. However, the fibrous masterbatch of Comparative Example 3 caused the phenomenon of melting and dripping after burning. The results show that the addition of polyimide can effectively prevent the mixture of polyetherimide and polyethylene terephthalate from melting after burning, and can achieve flame retardancy similar to that of pure polyetherimide. nature. As such, the present invention includes polyetherimide, polyethylene terephthalate, and glass transition temperatures between about 140 ^° C to about 170 ^° C, and 10% TGA loss temperatures between about 500°C. Fiber masterbatches of polyimide with viscosity between about 80 cP and about 230 cP when dissolved in NMP at 15 wt% solids between ^o C and about 550 ^o C have good flame retardancy And will not cause melting drop phenomenon.

In addition, after the fiber masterbatches of Example 2 and Examples 4-6 were produced, these fiber masterbatches were subjected to a melt-spinning process to manufacture the melt-spun fibers of Examples 9-14. Example 9

First, the fiber masterbatch of Example 2 was dried at 140 ^° C for 12 hours to remove moisture. Next, the dried fiber masterbatch of Example 2 was melt-spun at a melt-spinning temperature of 320 ^° C and a take-up speed of 800 m/min to obtain the melt-spun fiber of Example 9. (ie, pre-oriented filaments), wherein the fiber specifications of the melt-spun fibers of Example 9 are shown in Table 4. Example 10

First, the fiber masterbatch of Example 4 was dried at 140 ^° C for 12 hours to remove moisture. Next, the dried fiber masterbatch of Example 4 was melt-spun at a melt-spinning temperature of 345 ^o C and a take-up speed of 1000 m/min to obtain the melt-spun fiber of Example 10. (ie, pre-oriented filaments), wherein the fiber specifications of the melt-spun fibers of Example 10 are shown in Table 4. Example 11

First, the fiber masterbatch of Example 5 was dried at 140 ^° C for 12 hours to remove moisture. Next, the dried fiber masterbatch of Example 5 was melt-spun at a melt-spinning temperature of 345 ^° C and a take-up speed of 800 m/min to obtain the melt-spun fiber of Example 11. , wherein the fiber specifications of the melt-spun fibers of Example 11 are shown in Table 4. Example 12

First, the fiber masterbatch of Example 6 was dried at 140 ^° C for 12 hours to remove moisture. Next, the dried fiber masterbatch of Example 6 was melt-spun at a melt-spinning temperature of 345 ^° C and a take-up speed of 1000 m/min to obtain the melt-spun fiber of Example 12. (ie, pre-oriented filaments), wherein the fiber specifications for the melt-spun fibers of Example 12 are shown in Table 4. Example 13

First, the fiber masterbatch of Example 6 was dried at 140 ^° C for 12 hours to remove moisture. Next, the dried fiber masterbatch of Example 6 was melt-spun at a melt-spinning temperature of 345 ^° C and a take-up speed of 800 m/min to obtain the melt-spun fiber of Example 13. (ie, pre-oriented filaments), wherein the fiber specifications of the melt-spun fibers of Example 13 are shown in Table 4. Example 14

The melt-spun fibers of Example 13 were subjected to a thermal extension process at an extension temperature of 70 ^° C using a thermal extension braiding machine to obtain the melt-spun fibers of Example 14 (that is, fully extended filaments) with an extension ratio of 55%, wherein The fiber specifications of the melt-spun fibers of Example 14 are shown in Table 4.

Afterwards, the measurement of fiber size, fiber strength and fiber elongation was performed on the melt-spun fibers of Examples 9-14, respectively, and the melt-spun fibers of Examples 9-14 were evaluated for the droplet phenomenon. The descriptions of the aforementioned items are as follows, and the measurement results and evaluation results are shown in Table 4. < Measurement of fiber strength and fiber elongation>

The melt-spun fibers of Examples 9-14 were respectively fixed at a distance of 25 cm, and the fiber yarn tenacity tester (equipment model STATIMAT C, manufactured by TEXTECHNO) was used at a stretching speed of 125 cm per minute, and the tensile strength was 125 cm per minute. Fiber strength (g/d) and fiber elongation (%) were measured under the conditions of 100 Newtons (N), 65% relative humidity and 23 ^o C temperature. ＜ Evaluation of the droplet phenomenon＞

After each of the melt-spun fibers of Examples 9 to 14 were burned, whether there was a melt-dropping phenomenon was observed with the naked eye, and the evaluation results are shown in Table 4 below.

Table 4 Fiber Specifications Fiber strength (g/d) Fiber stretch (%) Melted or not Example 9 307d/96f 0.6 2.9 no Example 10 115d/96f 1.6 47.0 no Example 11 200d/48f 1.6 50.2 no Example 12 159d/48f 1.7 53.2 no Example 13 211d/48f 1.5 63.8 no Example 14 2.4dpf 3.0 35.4 no

It can be seen from the above Table 4 that the fiber masterbatches of Example 2 and Example 4-6 can be used for spinning under the condition that the melt spinning temperature is 320 ^o C to 345 ^o C, and the melt spinning with good mechanical properties can be prepared. spinning fibers. This result shows that compared to existing commercial polyetherimide meltspun fibers such as KURAKISSS ^TM manufactured by Kuraray co., ltd., the processing temperature is as high as 390°C , the present invention includes polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^℃ to about 170 ^℃ , 10% thermogravimetric loss temperature between about 500 ^℃ Melt-spun fibers prepared from masterbatches of polyimide fibers having viscosities between about 80 cP and about 230 cP when dissolved in NMP at 15 wt % solids to about 550 ^° C. Manufactured at a lower process temperature that can usually be achieved by the machine, so it has good applicability.

It can be seen from the above Table 4 that the melt-spun fibers of Examples 9-14 did not cause the phenomenon of melting droplets after burning. This result shows that the present invention comprises polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^° C to about 170 ^° C, 10% Tg loss temperature between about Melts prepared from fibrous masterbatches of polyimide having a viscosity between about 80 cP and about 230 cP when dissolved in NMP at 15 wt% solids between 500 ^o C and about 550 ^o C The spun fiber has a good flame retardant effect and does not cause dripping.

It can be seen from the above Table 4 that the melt-spun fibers of Example 14 obtained after thermal stretching have good mechanical properties and relatively fine fiber specifications. This result shows that, through the composition including polyetherimide, polyethylene terephthalate and glass transition temperature between about 140 ^o C to about 170 ^o C, the 10% thermogravimetric loss temperature is between about 500 ^o C C to about 550 ^o C, when dissolved in NMP and having a solid content of 15 wt % polyimide fibrous masterbatch having a viscosity of between about 80 cP and about 230 cP, the invention The melt-spun fibers can be thermally stretched to produce melt-spun fibers with good mechanical properties and further refined fiber specifications. That is to say, according to different process conditions (for example: coiling speed, extension temperature, extension temperature, extension ratio), the invention includes polyetherimide, polyethylene terephthalate and glass transition temperature between Between about 140 ^o C to about 170 ^o C, 10% thermogravimetric loss temperature between about 500 ^o C to about 550 ^o C, viscosity when dissolved in NMP and 15 wt% solids between about 80 Polyimide fiber masterbatches between cP and about 230 cP allow the production of melt-spun fibers of various fiber sizes with mechanical properties controlled within the desired range. In this way, the melt-spun fibers of the present invention have wider product applicability.

Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the appended patent application.

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Claims (10)

A fiber masterbatch, comprising: polyetherimide (PEI); polyethylene terephthalate (PET); and polyimide, wherein the glass transition temperature of the polyimide is Between 140 ^o C and 170 ^o C, the 10% thermogravimetric loss temperature of the polyimide is between 500 ^o C and 550 ^o C, and when the polyimide is dissolved in N-methyl At 15 wt% solids, the viscosities range from 80 cP to 230 cP. The fiber masterbatch according to claim 1, wherein the content of the polyetherimide is greater than or equal to 25 parts by weight and less than or equal to 80 parts by weight. The fiber masterbatch according to claim 1, wherein the content of the polyethylene terephthalate is greater than or equal to 20 parts by weight and less than or equal to 70 parts by weight. The fiber masterbatch according to claim 1, wherein the content of the polyimide is 1 part by weight to 5 parts by weight. The fibrous masterbatch of claim 1 having a melt index (MI) of 70 g/10min to 150 g/10min at 320 ^° C. A melt-spun fiber prepared using the fiber masterbatch according to any one of claims 1 to 5. The melt-spun fiber according to claim 6, wherein the fiber fineness is between 50d/96f and 220d/48f. The melt-spun fiber of claim 6, wherein when the melt-spun fiber is a pre-oriented yarn (POY), its fiber strength is greater than or equal to 1.5 g/d. The melt-spun fiber of claim 6, wherein when the melt-spun fiber is a pre-oriented yarn (POY), its fiber elongation is greater than or equal to 45%. The melt-spun fiber according to claim 6, wherein when the melt-spun fiber is a fully oriented yarn (FDY) with an elongation ratio of 55%, its fiber strength is greater than or equal to 3 g/d, and the fiber The elongation is greater than or equal to 35%.