DE2218137C3 - Naphthalate polyester fibers and processes for their manufacture - Google Patents

Description

-1.05 · ΙΟ ² · Ι »

+ 4.41 g DR S -0.95 · K) - · I "f 5.99

is determined. in the / 1 the birefringence of the unstretched Fibers means, as well as optionally the drawn fibers, between 0.01 and 10 seconds at a temperature of at least 140 C and below the melting point of the fiber material is further heat treated.

4. The method according to claim 3, characterized in that that the heat treatment is carried out on a heated feed roller.

5. Use of the naphthalate polyester bottle according to one of claims 1 to 4 for production of fabrics or flat insulation paint.

a medrige elongation and have _respects with h ^ hen temperatures below emerAbnahn ^ = _n.

_I ^included S ^rc ' ^c "' ^l r _hala , _po i _y csterfibers from the achievement of NJ £ hthaiaip y ^ ^

geruh «, the« nc gro ^ - ■ ·· ■ - _{ikcil bci hohcn}

before lower A ^b M ^h me ^de _Na h _{lhalalpo) ycstcr} . Temperatures al du. ^ UW ™ _f £ _{n Rir c} , _electric fibers have and gu_ ty. _{i (see above} . Insulating material ". ^ ^b ^^ _cr ^an " _cbr : _iU chlichcn naphthenic properties there , _high

, Halatpolyesierfäuren w ^ h _{DimcnsionssUlb} j, i _ia , Youngschcr Modul and r «customers,

compared to H.tze bcibeh ^ n ^ crystalline

that by d »c br iclun ^ an ^ _hUchcnNliph _

Structure by derjtni _f cn v- elongation

Naphthalate polyesterfa π mn an ^ ^ ^ ^

^StrukUlr ; t! From Sn c the fixed wedge at high Tcm

Cemass de.
polyester fibers ge

30 , door cck-

^ _{N hlhalal} . a _hlha , _a " _lcr ^

drive exhibit

after

the X-ray diffraction,,. _{; ründlini} .

40

50

The term refers to naphihalal polycarbonate fibers as well as a process for their production. In particular, the invention relates to naphthalate polyester fibers with a new crystalline structure, which is particularly suitable for electrical insulation materials are suitable and a process for the production of these fibers on an industrial scale.

Fibers made from Naphlhalatpolyesters through the reaction of naphthalene-2,6-dicarboxylic acid with AthyVnglykol are considered technical Materials, for example as rubber reinforcing materials. due to their superior mechanical and thermal relationships. compared with the fibers made from polythene terephthalail fibers, which were previously used on a large scale. known.

However, until now it has been assumed that the usual Naphthalene polishing fibers for such / wake are unsuitable for which these fibers are knitted, woven or non-woven fabrics at high temperatures and especially for electrical b.olicr materials are used Her main reason for this is that these NaphlhaUitpolyester the PO

ens

cS e «Γ, completion d -before, cn copolymcr.s.erter or ge-ηΐ h polyester is obtained. Ciecignote more KornmisLiuci } Yi-rbindumicn mil two F.ster bil-Si "; t H; Gppen , B aliphatic« D, -

, nelle groups. /. B. aliphatic Diwie Oxalic acid. Succinic acid. Adipic acid. alicyclic diacid. Cyclolalic acid,

"Ronruisehe" dicarboxylic acids such as phthalic acid. Iso-Sc. Naphthalene-IT-dicarboxylic acid or I), - nenvld carboxylic acid. DiphenyUi.hcrdicarboxylic acid. Kenyl sulfodiacid. DiphenoNvathandicar ·. hcnsä iodeiNatnum-ivdicarboxvbenzolsulonat. Carboxylic acids such as cilycolic acid. p-llydroxyben / oesiiure or ρ-llydroxyällioxyben / .. esai..e. Iy-Sh ₁₁ Kl _11n J, w> e l'mpylglykol. ^ ethylene-, vkol diethvl glycol. I et.amethylcnglycol. llexar ethvlendvkol. Neopen.ylenulykol. p-xylylene glycol, 4 !! - Vclohexanedimethanol. Bispheno Λ. pp-I inhen- "xvsiilfnn. 1.4-bis - (, .- h \ droxv; ilhox \ lben / ol. _._- bis-

(ρ · / »'- hydroxyethoxy phenyl l-propane. Polyalkylene glycol or p-phenylene-bis-ldimethylcycIohexani or their functional derivatives or high molecular weight compounds, those of the aforesaid Carboxylic acids. Hydroxycarboxylic acids. Hydroxy compounds or their functional derivatives derived are. Suitable further examples of third components are also (b) compounds with an ester-forming one functional group such as benzoic acid, benzoyl benzoic acid. Benzyloxybenzoic acid or Methoxypolvalkyienglvkol. (ei compounds with three or more acid-forming functional groups, such as Glycerin. Pentaerythritol or trimethylolpropane. The polyester can also be a matting agent such as titanium dioxide or a stabilizing agent such as phosphoric acid, phosphorous acid and their esters. Flame retardants and flame retardants.

The amount of the third component must not be greater than 15 molpro / ent. preferably not larger than 5 mole percent. If their proportion is 15 mole percent exceeds this often leads to a considerable decrease in the thermal stability. Fixed wedge. Elongation control or recovery of the bulk of the fibers obtained, and therefore must be excessive Quantities to be avoided.

The naphthalal polyester used according to the invention has an intrinsic viscosity d,) / between 0.3 and 1.0. The intrinsic viscosity is derived from the viscosity of the polymer measured with reference to a solution of the polymer in a 1: 4 ratio Phenol and o-dichlorobenzene at 35 C is obtained. When the intrinsic viscosity of the naphthalate polyester Exceeds 1.0, its melt viscosity becomes excessive high, making melt spinning difficult. If the intrinsic viscosity is below 0.3, own the resulting fibers do not have good properties.

The main characteristic of the fibers according to the invention is based on their novel crystalline structure. This crystalline structure is characterized by a diffraction intensity ratio [R) of 0.15 to 1.73 / between a Bragg angle of reflection 2 (-> - 18.7 and 2 <-> ~ 15.6 according to the X-ray diffraction method.

The invention is explained in more detail with reference to drawings. In the drawings shows

Y i g. 1 shows the distribution curve of the diffraction intensity in the equatorial direction of the naphthalate polyester fibers according to the invention and of conventional naphthalate polyester fibers. where dl ·: values are obtained from the X-ray diffraction method, and

F i g. Fig. 2 is a diagram showing the relationship between the heat treatment temperature and the heat treatment time. when a cloth made from the fibers of the invention is rinsed.

The measurement conditions of the in F i g. I represented the Beununus intensity curve were like l'oliit:

contraption

Divergen / spall. .

Stray piss

1 linear length. . .

Model D-9C Nickelliller.

35 kV. 20mA

0.15 m. ··.

0.4 mm

1,542 Λ

and Curve 2 shows the diffraction intensity distribution curve of the naphthalate polyester fibers in use. Curve 3 shows the distribution curve of the diffraction intensity of amorphous naphthalate polyester fibers.

The diffraction intensity ratio [R) between a Bragg reflection angle 2 (-) = 18.7 and 2 <-> = 15.6 is calculated using the following equation:

R =

Ic 18.7 - Ia 18.7
ic 15.6 - la 15.6

In Fig. 1 shows the curve of the glueing curve Hay minilensilate of the amber-like fibers.

where Ic 18.7 and Ic 15.6 are the diffraction intensities (height of the curve tip) at a Bragg reflection angle 2 (-> = 18.7 and 2 (-) = 15.6 in the distribution curve of the X-ray diffraction intensity of the fibers and Ia 18.7 and Ic 15.6 show the diffraction intensities of the amorphous fibers at a Bragg reflection angle of 2 (-) = 18.7 and 2 <-> = 15.6 in the distribution curve of the diffraction intensity.

As shown in FIG. 1, curve 2 has a high peak for the usual naphthalate polyester fibers with a Bragg reflection angle of 2 <■) = 15.6. However, the KiMve has no peak at 2 (-) - 18.7.

These polyester fibers therefore have a low diffraction ink silage ratio (R) of about 0.07. In contrast to this, curve 1 for the naphthalate polyester fibers according to the invention has a unique peak at 2 H = 18.7 and a diffraction intensity ratio (K | of about 0.55, which is considerably higher than the ratio for conventional naphthalate polyester fibers.

Due to their novel crystalline structure, as described above, the fibers according to the invention have sufficient strength and a higher elongation than the usual fibers. If the strength of the fibers is denoted by T (cd) and their elongation by E ("/ (iI), the fibers have a tenacity (as expressed by T · ['/ ·.') Of at least

2I.5. "Uih! The value for / ·; reaches 13 to 40" /, .. common naphthalene poly laser lasers with a ratio R of below 0.15 have a strength of about 5.5 g den. and their elongation is less than 15%. and their toughness is insufficient. On the other hand, when the value R exceeds 1.73, the elongation increases. however, the strength decreases. Therefore, Naph-Ihalalpolyeslerläsern with a K-value above 1.73 are also unsuitable.

The proper fibers have the advantage.

that their strength hardly decreases at high temperatures. For example, when the conventional naphthalene polyester fibers are treated in moist heat at 150 ° C for 6 hours, the wedge circuit is less than 50 ". However, when the fibers according to the invention are treated in the same way, the strength retention is about 55". or more The fibers of the present invention are also superior in light resistance.
Since the fibers according to the invention have a significantly improved elongation and superior heat stability and resistance to luminous heat and light, various difficulties can arise, such as the occurrence of fluff or decrease in strength during the healing of the lasers, for example when weaving oiler work, be avoided. These fibers give somi ^one textile products which are useful for clothing and for industrial purposes, in which Wärmebesländiukeil and loading

it is necessary to withstand damp heat. The fibers according to the invention can be applied to (wound your heat resistant wedge for workwear. I cppiche and covers for high temperatures. Hot gas filters and especially used for electrical Isoliermatcrialien. In addition, suitable These fibers are used in papermaking for single-wall materials or filier for hot water, there the fibers according to the invention have good resistance to moist heat.

The fibers according to the invention can take the form of continuous fibers, staple fibers, cables. Have yarns and bristles.

The fibers of the invention are obtained by heating undrawn yarns from a naphthalene polyester with a content of at least 85 mole percent ethylene-2,6-naphthalate units and an intrinsic viscosity between 0.3 and 1.0 and a birefringence (In) of 0.0275 or less, to a temperature between 112 and 170 C for the Duration of at least 0.43 seconds and thereafter. Stretching the yarns to a stretched amount (DR). which is defined by the following equation:

-1.05 ■ K) ² ■ I / i

4 4.41 S DR g 0.95 · H) '■ In 4 5.99.

The fibers are obtained, for example, in that the above-described polymer at a spinning speed of not more than 1500 m / min and are spun at a spinning temperature between 300 and 330 C to produce undrawn yarns with a Birefringence of not more than 0.0275 and that these yarns are fed around a feed roll that is heated to a temperature between 112 and 170 C, and that the yarns on the Roller to be heated for a period of at least 0.43 seconds and that then the yarn with a stretching amount of the following equation

-1.05 · 10 ² · in

+ 4.41 ^ DR ^ 0.95 · 10 ² · In +5.99

are drawn and that the drawn yarns are then heat-treated for a period of 0.01 to 10 seconds at a temperature of at least above 140 "C, but below the melting point of the yarns. If the spinning speed is relatively high, a heated one is below the spinneret The spinning chamber is provided, and the temperature of the atmosphere below the spinneret is kept between 0 and 400 ° C to adjust the birefringence of the yarn to 0.0275 or less, Of the above-mentioned drawing and heat treatment conditions, the heating temperature and the time before drawing have the greatest influence on the crystalline structure of the yarns: In conventional drawing with a hot drawing pin, the value R of the yarns is far below 0.15, since the heating before drawing is insufficient.

If the birefringence (In) of the undrawn yarns is greater than 0.0275, difficulties arise. even when the undrawn yarns are drawn with the above-mentioned draw ratio. When the stretching process is carried out with a relatively small ratio in the above range is, the yarns remain partially undrawn, and when the drawing process with a relatively large stretch ratio is made.

irelen lenses or thread breaks. Therefore no stable Sireck process can be achieved, and also the resulting yarns have a K value of below 0.15.

If the frying temperature is below 112 C before stretching, the stretching stress becomes excessive large, which causes excessive molecular orientation, which in turn reduces the K value to below 0.15 lowers, the purposes according to the invention not ίο are achieved. If, on the other hand, the support temperature before stretching exceeds 170 (. ', melt adhesion of the individual threads occurs, so that a stable stretching is not possible.

If the increase is shorter before stretching than 0.43 seconds, you get the same result that you get at a heating temperature below 112 ° C achieved.

If the draw ratio [DR) is below -1.05 · H) ² · In f 4.41, the K value increases above 1.73. and the strength drops below 4.4 g. The yarns obtained in this way are therefore less suitable. It is impossible because of the unstretched sections. C iarns with stable quality. When the "stretching ratio" increases over -0.95 · K) ² ■ I η + 5.99, the R-Wcrt decreases below 0.15 and the elongation becomes lower than 13%.

The novel naphthalate polyester fibers according to the invention become for use in a fiber cloth and for the fields of application specified above processed. The fiber cloth can easily go through contractions. Knitting, knitting or a method of manufacture made of felt or nonwovens, as is usual for other synthetic fibers. The processability in weaving. Works. Knitting or in the production of nonwovens or felts as good or even better than in the case of polyethylene terephthalate fiber. The appearance and handles of the resulting fiber towels stand up to any comparison with other synthetic fibers.

These good results can be attributed to the new crystalline structure of the fibers according to the invention, those to maintain sufficient strength and greater elongation than usual Naphthalate polyester fibers. The strength of the fibers that make up a fiber cloth, measured according to the Untangling the fibers shows only a decrease of about 10%. Furthermore, the R-Wcrl. the one measure for the properties of the crystalline structure is. only a few percent off. When fibers with an R-Wcrl of 0.65 are used, the disentangled fibers of the resulting fibrous sheet have an R value of about 0.61. This decrease is attributed to tension experienced during weaving. Working. Knitting or treatment for the production of felts or nonwovens.

As mentioned above, the fibers according to the invention can be made into woven fabrics of any desired texture are processed, such as plain weave, twill weave or satin weave, knitted or knitted Fabrics, such as circular knitted goods or non-woven fabrics, such as needle-punched, non-woven fabrics (fleeces) non-woven fabrics (bound fiber vlicse) or non-woven fabrics bound by spinning 65 fabrics. These fiber cloths can be woven, forfeited, knitted, mixed-woven or mixed with one another be spun. You can also go to movies. Foil or paper must be layered on top of one another.

The pulp then undergoes a treatment subjected to a "soap cooker", drum drying or heat treatment. Practice of this The heat treatment has a great impact on the properties of the fiber cloth obtained and on the Properties of the same in the subsequent treatment stages. namely shrinkage. Flatness and dimensional stability when exposed to heat.

The heat treatment conditions are determined by the heat treatment temperature (7 "C) and the Heat treatment duration (I in seconds) determined. It was found that the effective heat treatment temperature GcmäH of the invention at least. 21 (1 C. but below the melting point of the fibers should lie. A series of heat exposure time experiments was carried out on various Temperatures running. It was found that by the heat treatment of the fiber cloth under conditions satisfying the following two equations, a sheet of naphthalate polyester fibers which has superior heat resistance and mechanical strength wedge can be obtained and also has flatness, dimensional stability against heat and low shrinkage as well as has a uniform structure and is particularly suitable for electrical insulating materials. The above mentioned The equations are:

T -200 = 70c
7 '- 200 = 70 / - e

In this equation, c is the basis for the natural Logarithm.

F i g. 2 shows the relationship between the heat treatment temperature and the heat treatment time. The hatched section that differs from the above Equations !!) and (2) corresponding curves I and 11 shows a combination of the Heat treatment temperature and the heat treatment time, which are closely related to the properties of the heat-treated cloth. These properties particularly concern the Dimensional stability in heat, stability, shrinkage and flatness.

When this relationship between the heat treatment tcmpcralur and the heat exposure time is not met, d. h..wcnn the relationship falls outside the hatched section, are those Properties of the heat-treated fabric are unsatisfactory for practical purposes.

The untangled fibers that make up the heat-treated fibrous sheet that undergoes heat treatment was subjected to the above-mentioned temperature and time conditions, have a novel crystalline structure fundamentally different from that of conventional naphthalate polyester fibers differs. If the R value (measure of the crystalline structure) is not in the range between 0.05 and 1.5, the improved dimensional instability against Hitzx. the improved shrinkage and flatness of the fiber sheet cannot be achieved. If this R value is below 0.05, the fiber cloth has poor dimensional stability under heat and poor shrinkage behavior. and if the K-Wcrt exceeds 1.5, a fiber sheet having a grooved flatness cannot be obtained. Varnishes and Varnishes with similar finishing agents therefore cannot be uniformly impregnated into the resulting fabrics will. When the fabrics are cut into ribbons or strips, it is difficult to do them that way cut so that they have a straight edge. It also increases the strength of the fabric the following stages of development.

The heat treatment under the conditions of equations 1 and 2 can be carried out with the aid of a known

ίο Device, for example in a tenter frame be made (heat treatment device such as a fan oven or a heat treatment device of the roller type. The heat treatment can be either under tension or take place during limited shrinkage. Because the naphthalate polyester cloth is subjected to heat treatment while limited shrinkage tends to decrease strength, the Shrinkage should preferably be restricted to not more than 15% of the original length. When the shrinkage exceeds 15%, the above advantages can no longer be achieved. the The above-mentioned heat treatment can be carried out continuously during the further processing of the fibers, such as during weaving or rinsing or before or after converting the fibers into an end product such as electrical Isolicrmaterials, are made.

In the past, natural fibers, semi-synthetic fibers and synthetic fibers were mainly used as electrical insulating material in the form of fibers and fabrics. The fibers used support the technical development in the sectors of mechanical engineering, electrical engineering, communications engineering and electronics, as they have a constant quality and are available in sufficient quantities. These materials can be used continuously at temperatures up to 120 C (thermal resistance degree E). As materials which can be used up to 130 ⁰ C (Grad B) and 155 'C (degrees F), inorganic fibers such as glass fibers or asbestos fibers are to be applied in the processability. Suppleness, strength, toughness and handling are inferior. It has therefore been difficult to use B and F grades of electric and electronic equipments and machines and make them small in size.

Polyethylene terephthalate is a typical Grade E electrical fiber insulation material currently in use, but it does not have the Grade E heat resistance despite its superior processability and mechanical properties. Recently, aromatic polyamide fiber fabrics have been developed and used as organic fiber fabrics having sufficient heat resistance for impregnation insulation materials (at temperatures above grades B and F). This cloth is used after impregnating with a heat-resistant resin varnish. Such impregnated with LACV polyamide materials can Temperaturer above degrees F (180 degrees C. ⁰ H) withstand to have a superior resistance to chemicals Chemi. On the other hand, they are hygroscopic and have insufficient electrical and mechanical properties during or after impregnation with paint. Because of the large amount of space they occupy, these polyamide fabrics are inherently difficult to handle when used for wrapping compact parts.

509 685/2

9 ι 10

The naphthalal polyester laser material according to the invention is a much larger material have a sufficient heat resistance in terms of functionality than the usual mil lacquers possessed of the usual electrical fiber insulation painted cloth goods. This fiber isohermarial of grade B or F and have essentially lerial handling! »- and processing inherent superiority mechanical properties and an over-5 shank that is the same or even better than the floorboard Processability. You can get one of those common materials that are one Size and low weight have found a wide range of applications. The Machines and facilities contribute and can be achieved by the invention, impregnated with paint Grade F machines are used. Fiber cloth is also available with the usual, varnish-impriigned

Attempts have already been made to compare cloth goods impregnated with lacquer that are heat-resistant Provide naphthalate polyester fabrics that are meltable for grade F. The inherent lackdig and are pliable and a heat resistance of the impregnated cloth can also be considered an electrical insulation grade B and F have and their properties also used material, the far better mechaunler humid conditions in sufficient degree niche properties. Processability and quality to keep. It was found that such Naph-15 has.

thalatpolycsterstoffc can thereby be achieved. The electrical insulating means according to the invention can

that the Naphthalalpolycstersloffe with a varnish as a cloth. Fabric ribbon. Stol'f hose or as a sleeve in

the alkyl, polyurethane. Epoxy, acrylonitrile and form a simple fiber material made of naphthalal

Siliconarl or with a heat-resistant polyester fiber or as Lackluch. Lacquer cloth tape,

Varnish of the heterocyclic type alone or in a combination 20 paint towel tube or a pre-impregnated one

nation to be impregnated. Sehiehlmaterials in impregnated with a varnish

Examples of paints that are used in the context of the invention mold. The contradiction in the invention elck-

Can be used are alkyd paints. alkyd-Irish insulating material can also be used as a laminate or

modified polyurethane varnish ^ acrylic varnishes. alkydmo sold in the form of other articles of manufacture

differentiated silicone lacquers, alkyd-modified epoxy lacquers 25 spiral, which are bonded or melt-bonded

and other varnishes with high heat resistance. obtained by using an organic material

which corresponds to the substrate. Because the above- z. B. films, or an inorganic insulating material such as

called substrate hai good heat resistance. Glass. Can use asbestos or mica. The

give alkyd-modified silicone varnishes, alkyd-modified electrical insulating material can also be used for other bc-

dainty epoxy paints. Polyamide-imide varnishes. Pol- 30 special areas through storage of various

imide or vinyl fluoride polymers give better results. Antioxidants or Fenci retardants

One of the main features of the invention resides in this. be used.

that the naphthalate polyester cloth according to the invention will now be illustrated by means of examples

in particular with polyamide-imide, polyimide and vinyl- explain in more detaili.

fluoropolymer can be impregnated. The intensity in the equatorial direction according to the Rönlgcn-

Convenient substrate, which mainly consists of an or- diffraction process, the stress-uni-elongation curve

Ganic fiber, is of a high boiling point and the resistance iicuen over glowing heat

the polar solvent such as N.N'-dimethylform- using the following procedures

amide, N-methyl-2-pyrrolidone or N.N'-dimethyl- correct,

Acetamide attacked, especially on evaporation. 4.0

The usual substrate cannot be coated with an X-ray diffraction cover either
impregnated fabric with uniform quality device]) 9 (. "
be because of the heat shrinkage. The naphthalal 35 kV χ 20 ιηΑ. When using polyester cloth, the drying temperature is maintained with a thin nickel filter
about 200 C and has a sufficient 45 divergence gap 0 IS mm (.Λ
Shrinkage and a superior dimensional stability scatter gap Γ
lity and flat salvation. Therefore, if the above-described receiving gap; = 0.1542 A lacquer is used, the result is a cloth impregnated with lacquer of excellent quality. The ,-. ,,,
The above-mentioned paint can of course also be used for the glass load-elongation curve
fiber cloth or asbestos fiber cloth can be used. Length of the samples 20 cm
but the resulting impregnated cloth is not easy to pull .... 100 m min at 25 C pliable and very weak to bending. """ _ulll j _{cmcr rc} Uuivcn

The naphthalal-poly-moisture (RH) impregnated with the lacquer

cster cloth has superior mechanical properties. 55 _of (. 5%
like a great tensile strength, a great Young

modulus, a large tear, shear and bending die obtained from the stress-strain

strength. Furthermore, the impregnated with varnish has breaking strength and the decrease in the number of yarns

Naphthalate polyester cloth good thermal inherent (denier), which with the increase in elongation in to

shafts and dimensional stability. and related, have not been corrected.
sits stable electrical properties over you
wide temperature range. Furthermore, that from naph-

Thalatpolycster existing substrate cloth has a sufficient resistance '' ecen moist Hit / X
adequate resistance to various

Lacquers, insulating oils, freon, cooling oils, various 65 The sample was placed in water and b <

organic solvents and plasticizers. 150 C 6 hours lane in a closed vessel

By means of a suitable treatment based on the intended use (autoclave), the Fcsti]

A coordinated choice of varnish can maintain the fiber insulation properties of the sample.

! • Maintain electrical and mechanical parameters
of the mil l.aek impregnated cloth

1. Tensile strength and elongation

Fin tensile test was carried out in a room at 23 C and a relative humidity of 50 "" at a pulling speed of 2 (H) mm, min, the width of the specimen and the fin span length to 15 b / w. 150 mm has been set. The strength and the Elongation at break at break was measured (.IIS (-23181.

2. Mullen Resistance

S ^; e was measured according to .11ST-Sl 12 in a room at 23 (. 'and a relative humidity of 50 "Z ₁₁ .

3. Sehopper flexural strength

It was measured in accordance with JIS T-8114 in a room with 23 C and a relative humidity of 50 ",,.

Specific flow resistance

A fin potential of 500 full was applied to the sample at 20 C and the leakage current after one minute measured. The volume resistance is maintained by dividing the voltage by the amount of current shares (.11S (-2318).

The dielectric strength

Man UiIM the voltage from zero to the in one Increase in magnitude from 500 V see to 1000 V see. The dielectric strength is obtained by using the Voltage that causes a short circuit through divides the thickness of the sample (JIS C-2318).

example 1

Polyith) k-n-2.6-naphth.alate with an intrinsic viscosity of 0.65 was spun at 320 C through a spinneret, d: e circular nozzle openings with had a diameter of 0.46 mm. The elicitor Thread was wound up at a speed of 800 m min. F. a 20 cm long heating chamber was located immediately below the spinneret, and the atmosphere below the spinneret was held at 315 C. The resulting yarn of 24 threads with a titer of 400 den with a birefringence of 0.0120 was wound up and

Table Il

with 8 turns around a heated feed roller with a diameter of 90 mm and Pre-heated on the roller and then stretched 4 times. Then the yarn was using a slit mold heated to 250 "C stretched and heat-treated. The resulting (iarn was taken at a speed of 530 m min wound up. The 1 properties of the yarn obtained are summarized in the following table I:

label I

Ylt-
No. lenipe
r.tUir der
Supply K ice cream wedge strain 2 / ahi ual '/ e ! Cl Ig denl l ", i | 1 115 0.60 5.61 22.K 26.8 1 130 0.63 5.68 22.9 27.2 3 145 0.70 5.66 23.6 27.5 B. ρ i e 1

Polyethylene-2,6-naphalate with an intrinsic viscosity of 0.60 was melt / spun at 315 ° C. with a spinneret, the circular nozzle openings with a diameter of 0.4 mm. The resulting thread was traveling at a speed from 600 m min recorded. There was a 10 cm long heating chamber directly under the spinneret and the atmosphere under the spinneret was kept at 270 ° C. The resulting imueststretched 48 thread yarn with a liter of 400 den. with a birefringence of 0.0150 was picked up and heated for different / partial spans on a feed roller that heats to 145 ° C had been. The yarn was then stretched with a slot heater heated to 250 ° C. Thereupon was the yarn at a speed before 600 m min recorded. The stretch ratio was changed this time, and the! Properties of the see The yarns giving rise to it are listed in Table I below.

Posting Back IIci / line k 1 esligkcil IVhmniL ' lcsiigkeiisbeibch aging / älugkeil No. \ erh.illius Keel I; j the I. I "η I I "'ill 111 hit / c ") in Liehr ") 4th 3.3 1.36 1.02 5.20 30.6 73.6 80.9 28.8 5 3.6 1.48 0.99 5.48 29.7 71.8 79.0 29.9 6th Λ.9 1.6! 0.79 5.62 24.9 69.3 75.0 28.0

*) (islündii.e treatment in ieuchler llit / c hei Ι ^ς ι> I.
**) iOstiindigc irradiation with a lamp.

Comparative example 1

The undrawn yarn obtained according to Example 2 was with e no stretch ratio of 3.3. 3.6. 3.9 and 5.0 stretched using a hot peg and hot plate. The preheating time was 0.11 seconds, the temperature of the streek pin 155 C and the temperature of the plate 200 C. That

Yarn was then taken up at a speed of 600 m min. The! Results are
Table 111 compiled. The baked goods obtained were not transparent and had a hardness of 4.4 g and more. These garments had a toughness that was below 21.5. and 1 X-ray diffraction intensity ratio ( R |. das un
0.15 fan.

13 \

14th

a belle HI er-uch No. Slreckverhä! ·: »* R

lcslmkeil elongation toughness sireckbark wedge

lü dm! ("u)

3.3

0.13

4.72

18.1

20.1

contained unstretched sections

3.6 0.08 5.24 14.2 19.7 Well 9 3.9 0.05 5.73 10.1 18.2 Well η 5.0 7.11 7.0 1p.7 frequent thread breakage

Comparative example 2

The procedure of Example I was repeated except that the heating chamber was below the spinneret missing. A straight yarn with a birefringence of 0.033 was fed at a speed of 1100 m min recorded. The results are shown in Table IV below.

Table IV

N ersuch temperature stretching R

No. of the / ufeit- ratio

VALUE / E

I C)

1 eslmkeit elongation toughness sircckh.ukeil

145

2.8

0.13

Ig ilen) (".Ί

6.6 10.7

21.6

frequent thread breakage

Example 3

The procedure of Example 1 was repeated with the modification that the hot / tcmperatur the roller was au 5 C. The stretch ratio was changed to 3.0. 3.5. 4.2 and 5.0. The results are fine

in the following table V y.

Table V

i no. stretching ratio R

readability elongation toughness elastic wedge

(u den I ι "<Ί

12th 3.0 1.93 4.25 44.0 28.2 contained unstretched Sections 13th 3.5 1.06 5.21 28.3 27.7 Well 14th 4.2 0.44 6.26 18.2 26.7 Well 15th 5.0 0.12 7.10 10.5 23.0 sometimes they broke thread

Note.ii. The experiments referred to in serial numbers 12 and 15 are comparative experiments.

Example 4

The procedure of Example 1 was repeated except that the draw ratio was set to 4.8 a was changed. The results achieved are summarized in Table VI:

Table Vl Temperature of R. I estiiikcii Dchmmp / ähigkcit Attempt no. /.ufülmingswal/e I Cl I y den) I ". I 110 0.12 5.0 12.0 17.3 16 115 0.16 5.86 14.0 21.9 17th 130 0.28 6.49 I 5.0 25.1 IK 145 0.33 7.02 16.2 28.3 19th

Ληιικ'ΐ k iiti'j IKm unlei der tiiittciHlcn number IC »uefiihrk * Vim Mich im cm VcitI

15 16

Example 5

The procedure of Example 1 was repeated except that the temperature of the heating feed roller to 145 ° C and the temperature of the Schlitzerhitzors was changed to 280 ° C. The Vorerhilzunastenipcratur has also been changed. The results are summarized in Table VH:

Table VII

search N r. Mrcck-
ratio Hei // eM
(soul R. I esligkeil
(g the) strain
("Oi t'esligkcib
(%) ; supplementary statement toughness in Hil / e ·) in light ") 20th 4.0 1.36 0.42 5.70 17.6 69.6 75.9 23.9 21 4.0 0.40 0.11 5.50 12.5 45.7 56.9 19.4

Note: The experiment carried out under serial number 21 is a comparison experiment.
*) iislündigc treatment in moist llit / c vein 150 C.
**) 5i) sliJ »i) i _ !. 'L- irradiation with a Xe» nn) a; npe

Example 6

The procedure of Example 1 was changed to 145C with the Ab-. The stretch ratio

change repeated that the time for heating and the heating time were also changed. Which he-

of the unfortunate (iarnes with the feed roller aimed at I ^{: the} results are summarized in Table VIII.

was spent on I.2H. 1.41. 1.54. 1.66 and 1.79 25.
Seconds and the temperature of the feed roller / e

"label VIII

Ver
search
No. Stretch
ratio Hei / veit
in see R. l'esliy-
speed
(g the) strain
(",.) 3.0 I.2S 2.52 3.0X 43.9 23 3.3 1.41 1.02 5.20 30.6 24 3.6 1.54 0.79 5.62 24.9 25th 3.9 1.66 0.42 5.70 17.6 26th 5 2 1.79 0.091 7.49 6.2

Note: The experiments under serial numbers 22 and 26 are comparative experiments. The drawn yarn
were 47.5 den 25 yarns.

Each of these draw yarns was twisted, sneaked, and the residual size adhered was less

tet and stretched to form a warp thread and 0.2%. Then the cloth was uni at 120 ° C

In one shot step, package delivery, Italian drum drying were subjected. The cloth was practiced

Twisting and weft bobbin winding are carried out in a 15 cm long stenter frame at one speed

men. around a woven cloth with a width of digkeit of 20mmin and at a temperature before

101 cm to form. The Ketl and weft thread dichle 50 230 C out and at a stretch of ΓΊ

was 72; <31 2.54 cm. heat mixicrl. around a woven naphthalate cloth

The woven cloth was manufactured under the following conditions: polyester. The density of the ketl- um

rinsed: weft threads were 74 × 32.5 / 2.54 cm.

The cloth was tied in a loop in hot water. The properties of the woven cloth are in de

cooked, which was kept between 90 and 100 C. 55 Table IX below.

Table IX

(icstiecklc (iirne experiment Ni

22 2 <24 2s 2 (i

Try Ni

27 2S 2 ') 111 Il

Tensile strength (kg cnrl warp thread weft thread

12!) 750 900 1100 I 250 I IO 690 SOO 1050 1240

continuation

Stretched yarn Attempt no.
■>■> 23 24 25th 18th
19th 2 » H 1 ° Attempt no.
27 2S 29 30th 18th
16 31 15th
13th Tensile elongation (%)
Warp thread
Weft 60-80
55-75 27
35 23
30th 0.9 <
1.0 < 0.1
0.1 Tensile elasticity (■ 10 ³ kg / cnr)
Warp thread
Weft 1.2
1.1 15th
Il 17th
12th 0.30
0.25 0.025
0.022 Elemendorf - tear strength (kg)
Warp thread
Weft 0.3
0.2 1.0 <
1.2 < ! 7 < Λ value of the untangled threads
Warp thread
Weft 1.92
1.81 0.95
0.86 0.65
0.70

B e i s ρ i e

The procedure of Example 1 was repeated except that the temperature of the feed roller was changed to 130 C to produce 50 denier weft bobbins.

39 wefts were doubled, laughed and subjected to a weaving process. In a warp step, bobbins were delivered. Twisting and twisting and drawing were carried out, and in the weft stage, bobbins were discharged. Twisting and filament winding executed. This produced a woven cloth with a width of 101 cm. The warp and the weft density at this point was 72: <31 2.54 cm. The obtained woven cloth obtained was boiled in warm water in a loop.

Table X

that was kept between 90 and 100 C. The menu at Resllichiemmittel was on less 0.2% decreased.

The woven cloth was in a 15 cm long tenter frame at various temperatures unc Speeds heat elixiri. A naphthalene polyester woven cloth having a width was obtained from HX) cm. The cloth was suitable for an electrical insulating material. The Kelt- and Sehussfadendichli at this point was 74 χ 32.5 2.54 cm. Ver Different heat treatment conditions and properties of the obtained woven inch are ii Table X together. The stretching is sad at this point ΓΌ.

Attempt no.
32 13th 30th 34 50 35 Temperature (C)
200 2 «) 74
32.5 230 74
32.5 26> / eil I sec I
5 II) 900
850 45 900
800 1200 properties
Titcr of the finished yarn 50 23
27 25th
30th 50 Density (number of threads per 2.54 cm)
Chain
Shot 74
32.5 IS
14th 17th
13th 74
32.5 Tensile strength (kg enr)
Chain
Shot 120
IK) 950
820 Elongation ("i. |
Chain
Shot 2.0
2.0 ¹ O
12th Tensile elasticity (K) ¹ kg enr)
Chain
Shot 1.2
Il 18th
15th

continuation

20th

Attempt no. 0.2 260 IU Well 34 1.2 Well 35 1.0 32 0.3 1.5 10 1.6 13th 1.2 Tempcniinr ι f Ί 1.0 IO 8th Π 231) 8th 14th 265 8th 2 <X> 50 8000 85 (K) 8 (KK) Zeil (see) 35 3000 45 4 (MK) ! 2 (K) 3000 5 8th 1.5 2.0 2.0 small amount small amount 1.0 6th 1.5 8th

Elemendorf tear strength (kg)
Chain
Shot
Mullen Burst Strength (kg cm ² )

Schopper flexibility
(Number of bends)

Chain

Shot

Shrinkage in dry hil / c

at 250 C for 60 min

Flatness viewed with the naked eye

Addition after 90 days of heating
at 210 C ^

Chain
Shot

Note: Experiments Nos. 32 and 35 are comparisons, if the varnishchaiulhinjislenipcraturcn within the Range lie, the du κ Ii the equations II) and (2) is defined

As shown in 1 "abelle X, hold onto the cloth Experiment No. 32 in which the worm treatment time is shorter than that required by equation (1) was. low strength, large shrinkage, low flatness and one R value of 0.02. Further, the cloth obtained by Experiment 32 was for an electrical insulating material not suitable. In contrast, the cloth after tests 33 and 34, which correspond to equations (1) and (2) sufficed, good heat resistance, one good strength retention, low shrinkage, good flatness, and an R-Wcrl of 0.50. The cloth samples after Runs 33 and 34 formed a superior electrical insulating material.

In experiment no. 35. in which the worm treatment time was longer than indicated in equation (2). were the properties of the obtained The cloth was no worse, but the cloth had a bad workability. In addition, is a such long heat treatment not economical.

Example 8

Polyethylene-2,6-naphtha !ate with an intrinsic viscosity of 0.70 was spun according to Example 1 Schmcl / .sponnen, the temperature of the feed roller at 145 C. The resulting drawn yarn was woven and washed for 40 seconds Long subjected to a heat treatment at 24O'C. A woven naphthalate polyester sheet was produced with a Kelt and weft thread density of 85 χ 43 / 2.54 cm. The cloth was subjected to a heat deterioration test exposed in air at high temperatures. The results are in Table XI compiled.

It was found that the resulting cloth was also used as a 155 "C heat-resistant material can be.

Table XI

Properties after aging for 30 days at 230 C gear aging testing machine

Itücnsch.iHcn Aiuangs- To ttert 3U1aucn hot 23ΪΙ C Titer of the finished yarn (den) 100 100 Density (number of threads / 2.54 cm) Chain 85 85 Shot 43 43 Tensile strength (kg / cm ² ) Chain 1200 950 Shot 900 800 Tensile elongation (%) Chain 24 15th Shot 32 18th Approval (10 ^! Kg / cm ² ) Chain 16 16 Shot 14th 14th Elemendorf tear strength (kg) Chain 1.6 1.5 Shot 1.5 1.5 Mullen Burst Strength (kg / cm ² ) 8 < 6th Schoppe r flexural strength (Number of bends) Chain 12,000 9,000 Shot 11,000 5, (K) O Dimensional stability (%) Chain 100 97 Shot 100 96

21

ίο η /

Usage example Λ

A lacquer made from a polymer of an alkyd resin and methylphenylsiloxane was made into a subcloth let in, made of a woven Naphlhalalpolycstertueh which had been prepared by a method in Example 8, followed by drying at 120 ° C for 7 minutes. Thereupon the cloth was heated dry at 200 ° C. for 26 minutes. The amount of the impregnated lacquer io shows that the comparative example no ι was 2.7 times the amount of the substrate cloth. Results hold.

Table XII

For comparison purposes, the above author; with the amendment repeated that an is Naphthalal polyester covers a woven cloth made of polyethylene / terephthalate yarn (100 den 24 egg has been used. The results were compared with the above results. The results compiled in Table XII. From the Tu

Kiüenxehaflen

Tensile strength (kg cirr) (15 mm width) Tensile elongation (%) (15 mm width) Schoppcr flexible wedge (number of bends) MuIlcn breaking strength (kg cm ² ) Specific volume resistance (Ohm-em) Dielectric strength (Kv mm)

Usage example B

An alkydmodilizierler F.poxylack was in a strattuchcs. The cloth was lani for 5 minutes;

Subslrattuch let in, which dried from a woven 150'C.

The cloth impregnated with the varnish had dii

driving in example 8 was won. The set 35 features: of the paint was 2.7 times the amount of sub-

(icm; il.t ilci I ι lim ιΐιιπμιιημ VciulcichsuTMidi after 7 doors
at 21 (1 C ΛηΙίίημχννοϊΊ after 7 ropes
at 210 (' Beginnerswcrl 20 (1 ¹ X) O 600 7 (K) 4th 25th 16 35 Completely
destroyed K) - ¹ < XOO Uf-. 13th H < d 8 <- 4.1 · H) " 3.4 x 10 " 3.1 10 " 3.4 · H) "

54

For this 2 Initial After 7 Taiicn at 210 C Tensile strength (kg / cm ² ) 850 595 Tensile elongation (%) 17th 15th Schoppcr-Bicgc- strength about 800 about 720 (Number of Bends) Mullcn Burst Strength 9 < 7th (kg / cm ² ) Specific through gangswidersland 5 ■ ΙΟ ¹⁵ 4 · 10 ^ls (Ohm / cm) Dielectric Dia impact resistance 60 55 (Kv / mm) Sheet drawings

Claims (3)

Claims: IO 1. Naphthalate polyester fibers, characterized in that they consist of a naphthalal polyester which contains at least 85 mol percent ethylene-2,6-naphthalate units and has an intrinsic viscosity of 0.3 to 1.0, and that the fibers have a diffraction intensity ratio (i?) Of 0.15 to 1.73 between a Bragg reflection angle of 2 θ = 18.7 and 2 θ = 15.6 ° according to the X-ray diffraction method. That after a six-hour heat treatment in wet steam at 150 ⁰ C have 2. Fibers according to claim 1, characterized in that a residual tensile strength of at least 50%. 3. Process for making the naphthalate polyester fibers according to claim 1, characterized in that the unstretched naphthalate polishing fibers, which have an intrinsic viscosity of 0.3 to 1.0 and a birefringence of not more than 0.0275. For 0.43 seconds at a temperature of 112 to 170 ° C heat-treated and then drawn, where the draw ratio (DR) is given by the equation