JP2841905B2 - High strength paper from floc and fibrid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Wet-laid nonwoven sheets of synthetic polymer fibrids and short lengths of staple fibers are:
It is known from U.S. Pat. No. 2,999,788. The bonding of these sheets can be obtained by heat and / or pressure. As taught in the aforementioned patents, fibrids form a solution of a polymer, preferably in an aqueous medium,
Prepared by shear precipitation. In general, fibrids are produced by the papermaking technology used with wood pulp.
Converted directly to nonwoven sheet structure or paper. Preferably, the aqueous mixture used to prepare the nonwoven sheet by the papermaking method will include short fibers or flocs in addition to fibrids. Other materials can be added as needed.

The nature of the flocs and fibrids and the interaction between them, of course, determines the nature of the sheets and the end use applications in which they can be applied. It is an object of the present invention to obtain a sheet exhibiting high strength and high glass transition temperature (Tg). Some of the new sheets also show remarkable electrical properties.

[0003] The present invention relates to 90 to 10% by weight of the following units:

[0004]

Embedded image

Wherein n is 4 or 5, and X is 0.0
1 to 0.50, and Ar is 3,4′-oxydiphenylene, 4,4′-oxydiphenylene, 4,4 ′
-Sulfonyldiphenylene, 1,3-phenylene, 1-
Methyl-2,4-phenylene and a group selected from a mixture of such groups or a mixture of up to 50 mol% of 1,4-phenylene groups based on a mixture of such groups with groups, A high-strength sheet structure consisting essentially of 10-90% by weight of flocs of carbon, aramid or glass fibers held in place with essentially composed fused fibrids. The novel fibrids are also part of the present invention.

The sheet product of the present invention is a wet-laid, hot-pressed sheet of flocs of carbon, aramid and certain novel fibrids.

The term "flock" is used to describe short fibers, such as those commonly used in the preparation of wet-laid sheets. Flocks suitable for use in the present invention typically have a length of less than 2.5 cm. In embodiments, the fibers of the flock are 2.
It had a linear density of 2 dtx and a cut length of about 0.68 cm. Such flocks provide the resulting sheet with maximum strength and shrink resistance.

[0008] Fibrids have very small, non-granular, flexible, fiber or film-like properties. At least one of those three dimensions has a small size with respect to the largest dimension. They are prepared by precipitating a solution of the polymeric material using a non-solvent under very high shear. Suitable fibrids and methods for their preparation are described in US Pat. W. Morgan
U.S. Pat. No. 2,999,78 issued to U.S. Pat.
No. 8 is described. Fibrids are always prepared as a dispersion in a liquid. They can be converted to an aqueous slurry by a suitable washing technique. Fibrids characteristically have a high absorption capacity for water and have a sufficiently high strength when deposited on a screen, even when wetted and ready to be processed on a paper machine.

A suitable sheet is to deposit an aqueous slurry of the papermaking fiber material uniformly on a perforated surface (eg, a fine mesh screen or fabric) and to rapidly drain much of the water through the perforated surface. To form an initial sheet. Sheets once prepared on a laboratory scale paper machine are labeled "handsheets".

[0010] The fibrids used in the present invention are prepared from polymers having the following repeating units in the indicated proportions:

[0011]

Embedded image

Wherein n is 4 or 5, and X is 0.0
1 to 0.50, and Ar is 3,4′-oxydiphenylene, 4,4′-oxydiphenylene, 4,4 ′
-Sulfonyldiphenylene, 1,3-phenylene, 1-
Methyl-2,4-phenylene and a group selected from mixtures of such groups or mixtures with up to equimolar amounts of 1,4-phenylene groups based on such mixtures of groups and groups. The following examples, except for the control, are illustrative of the present invention and are not intended to be limiting.

[0013]

【Example】

Example 1 This example describes the use of a polymer having the following repeating units of the present invention in Applicant's co-pending U.S. patent application Ser.
Prepared according to the procedure of 2,295.

[0014]

Embedded image

About 36 g of polymer (intrinsic viscosity 0.5)
Was combined with 264 g of dimethylacetamide (DMAc) containing 4% LiCl to prepare a 12% polymer solution. This solution was heated to 85 ° C. to dissolve the polymer, yielding a clear, light brown / gold solution.

In a Waring 7011 blender (31BL02), 50 ml of DMAc (4%
Of LiCl) and 200 ml of distilled water. Using a blender operating at high speed, 75 ml of the polymer solution was slowly injected into the top of the blender (approximately 0.3 cm wide flow at the top of the blender). The resulting fibrids are purchased from Whatman Internationala.
l Ltd. ) Vacuum filter on # 4 filter paper and add about 50
Excess DMAc was removed by washing 5 times with 0 ml of water.
The resulting fibrid cake was dried.

Example 2 This example illustrates the preparation of a nonwoven sheet structure of the present invention using the fibrid and aramid flocs of Example 1. The floc was prepared from paraphenylene terephthalamide fiber (PPD-T) Kevlar 29 fiber from E. I. Dupont.

70% by weight of fibrids and 30% by weight
Hand sheet wo, 683 containing the aforementioned floc
Prepared from 0.1 ml of a 0.32 cm (0.125 inch) floc of slurry of 0.3 ml solid fibrid and 1.1052 g. Fibrids and flocs and 2400 ml of water were added to a British Pulp Evolution Apparatus (British Pulp E).
evaluation Apparatus) [Mavis Engineering Limited
nearing, Ltd. ) No. 8233]
Then, by dispersing them for 5 minutes, a hand sheet was manufactured. This material was added to a Noble and Woods handsheet mold and additional water was added. The stock solution was stirred 10 times with a stir plate and then drained under vacuum through a screen (100 mesh screen) with a 0.15 mm diameter screen opening. The sample was laid between two ply (each side) blotters to remove excess moisture. The handsheet was then transferred to a blotter by quickly placing the sample and screen on the tabletop. The samples were dried on a handsheet hotplate drier (Noble and Woods, No. F10). The strength of the sample was determined to be sufficient for production on a fold linear paper machine.

Hot pressing the handsheet [Pharrell
Watson-Stillman (Farrel Watson-
Stillman), no. 9175-MR type] for 1 minute. The samples were measured according to ASTM D-828 and had a breaking strength of 0.52 N / m width (29.44 lb / inch width) and 4227 MPa (613 kps).
It was determined to have a modulus of i).

Example 3 This example uses the fibrids of Example 1 in the manufacture of a sheet structure having several different types of flocks. In some cases, the ratio was changed. Item G is metaphenylene isophthalamide (MPD-I)
Is a control using fibrids. Items A and B use flocks similar to that of Example 2, while items E and F use aramid flocks from MPD-I fibers.

Using the same method of making the formed paper of Example 2, the handsheets of items BF were made having the following composition:

[0022]

[Table 1] Item type of fiber% flocks% flocks Length cm (inch) A 70 30 PPD-T 0.32 (0.125) B 60 40 PPD-T 0.32 (0.125) C 60 40 CARBON 0.32 (0.125) D 70 30 CARBON 0.32 (0.125) E 60 40 MPD-I 0.64 (0.25) F 70 30 MPD-I 0.64 (0.25) G 60 40 MPD-I 0.64 (0.25) All papers have sufficient strength to be manufactured on a paper machine. It was determined to have.

All of the handsheets from above were hot pressed (Pharrell Watson-Stillman, No. 91).
75-MR type), 6.895 MPa (1000 ps)
i) Pressed at 279 ° C (535 ° F) for 1 minute. The properties are described below.

[0024]

[Table 2] Breaking strength, N / m normalized modulus, normalized item (lb / inch width) Breaking strength, N / m MPa (kpsi) modulus, MPa A 0.52 (29.44) 0.39 4227 (61 3.53) ) 3230 B 0.38 (21.97) 0.26 2819 (40 8.80) 1977 C 0.11 (6.28) 0.19 562 (81.47) 972 D 0.20 (11.37) 0.34 818 (118.70) 1385 E 0.34 (19.25) 0.18 2164 (31 3.83) 1143 F 0.29 (16.85) 0.14 2282 (33 0.92) 1118 G 0.28 (16.15) 0.14 1584 (22 9.93) 798 Breaking strength and modulus were "normalized" to the same density and basis weight as the control in item G. Carbon paper will not be as dense as rigid fibers under the same pressing conditions. As can be seen, items AF are better than item G.

Example 4 Approximately 50 pounds of the polymer of Example 1 (0.5-0.6 intrinsic viscosity) was combined with sufficient DMAc (4%) to form a 30% solids solution. In LiCl). The above 30% solids solution was prepared according to US Pat.
No. 018,091. The resulting fibrids are washed with water and D
The MAc and chloride content are reduced to about 1.0% and 0.3%, respectively, based on the polymer.

25.4 pounds of fibrids were placed in a hydrapulpler at 25.2 pounds of 0.64 cm.
(0.25 inch) PPD-T flock and 37
Add with 62 l (994 gallons) of water and add 15
Dispersed for minutes.

This material was diluted to 0.35% solids and then double disc refiner [Sprout-Waldron 12 "Twin-Flo, Model No. 12-MA, Line No. 67-1432) to a standard fold linear paper machine at a rate of 4.26 l / min / cm width (2.86 gallons / min / inch width) to provide 27.2 kg / min.
A 914 m (60 lb / 3000 ft) sheet was formed at a wire speed of 50 ft / min. The sheet was dried to a moisture level of 1.15%.

The breaking strength and modulus values of the paper and of the papers relatively made using MPD-I fibrids are described below for the machine direction MD and cross direction CD.

[0029]

TABLE 3 breaking strength, N / m Modulus, item fibrids (lbs / inch width) MPa (kpsi) MD CM MD CM polymer on a 0.04 (2.34) 0.03 (1.55 ) 95 (13.77) 46 (6.68) b MPD-I 0.10 (5.58) 0.06 (3.38) 265 (38.41) 126 (18.30) Hot-press a sheet sample (Pharrell-Watson-
Stillman, no. 9895-MR) and 6.895
Pressed at 1000 psi (MPa), 535 ° F. (279 ° C.) for 1 minute.

The breaking strength was measured and is shown below. MP
Data for papers relatively made using DI fibrids and flocs of PPD-T are included as controls.

[0031]

[Table 4] MD breaking strength, CD breaking strength, MD modulus, CD modulus, Item N / m (lb / N / m (lb / MPa (kpsi) MPa (kpsi) inch width) inch width) a 0.47 ( 26.98) 0.36 (20.65) 3286 (476.56) 2380 (345.24) b 0.28 (16.09) 0.20 (11.31) 1174 (170.25) 438 (63.51) As can be seen, fibrids were used for both items a and b. , The fibrids of item a result in a substantially improved sheet. It would be expected that a similar improvement would be obtained if glass flocks were used instead of the aramid flocs of items a and b.

Example 5 In this example, fibrids were prepared from a polymer consisting essentially of the following repeating units in the moles or ratios indicated.

[0033]

Embedded image

Where Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene groups, and a floc of PPD-T was used.

The copolymer was prepared in a 2 liter resin bottle equipped with a stirrer, heating mantle and continuous nitrogen flow. IBC (862.5 g, 2.4 mol), MP
D (183.2 g, 1.7 mol) and PPD (78.
5 g, 0.73 mol) at 250 ° C. and 260 ° C.
Maintained at a temperature of ° C for 4 hours. The clear amber plasticized copolymer prepared in the solution containing residual caprolactam was cooled to room temperature. The copolymer has an intrinsic viscosity of 0.
8 and its Tg was 217 ° C. Its proton NMR spectrum indicated that X was 0.27.

6 g of the above polymer was converted to 440 g of DMAc
(4% LiCl) were combined to form a 12% polymer solution. This solution is heated to 85 ° C. to dissolve the polymer and give a clear, light brown / gold solution.

The Waring 7011 blender is 50 m
DMAc (4% LiCl) and 200 ml distilled water. Using a blender operating at high speed, 75 ml of the polymer solution was slowly poured into the top of the blender (about 0.3 cm at the top of the blender).
Width flow). The fibrids (fibrid A) are vacuum filtered and washed five times with about 500 ml of water to remove excess DM
Ac was removed. The resulting fibrid cake was dried.

219 g of the cake of this fibrid was added to 21
Mixing with 81 ml of water produced a slurry of 1.2% solids. This slurry was treated as described in Example 2 with 5
Dispersed for minutes. 750 ml of this fibrid slurry was added to 2250 ml of water to produce a 0.3% solid slurry. Commercial blender whirling 0.3% fibrid slurry (CB-6, type 33BL12)
Scoured at high speed for 30 seconds in the medium.

An additional sample using MPD-I fibrids (Fibrid B) was processed for the same slurry preparation and scouring steps.

683 ml of a slurry of 0.3% solid fibrid and 1.1052 g of 0.125 cm
(0.05 inch) PPD-T floc was used to make a handsheet consisting of 70% fibrid A / 30% PPD-T floc. Add fibrids and flocs and an additional 2000 ml of water to the British Pulp Evolution Apparatus.
sh Pulp Evaluation Appara
tus) [Mavis Engineering, Ltd.]
o. 8233] and dispersing them for 5 minutes to produce a handsheet. This mass was added to the handsheet mold and additional water was added. This raw solution was stirred 10 times with a stir plate, and then 0.15 mm
Screen with a screen opening of diameter (100
Vacuum drained through a mesh screen). The sample was laid between two ply (each side) blotters to remove excess moisture. The handsheet was then transferred to a blotter by quickly placing the sample and screen on the tabletop. The sample was dried on a handsheet hot plate dryer. The above MPD as a control
A similar sample was prepared using a slurry of -I fibrids.

The breaking strength and modulus values of the paper and of the paper made comparatively using Fibrid B are listed below.

[0042]

TABLE 5 Break Strength, Modulus, fibrids N / m (lbs / inch width) MPa (kpsi) A 0.03 ( 1.75) 72 (10.51) B 0.15 (8.50) 219 (31.80) then the handsheet hot pressing 6.895M
Pressed at Pa (1000 psi), 279 ° C (535 ° F) for 1 minute.

The breaking strength and modulus values of this paper and of the papers relatively made using MPD-I fibrids are described below.

[0044]

[Table 6] Example 6 This example is a control showing the use of thermoplastic polymer fibrids.

30 g of polyetherimide (PEI, U
LTEM 1000, G.I. E. FIG. 270 g of polymer
And a 10% polymer solution. This solution is heated to 85 ° C. to dissolve the polymer and give a clear, light brown / gold solution.

In a Waring blender, add 50 ml of DM
Ac (4% LiCl) and 200 ml of distilled water. Using a high speed blender, 75
ml of polymer solution was slowly poured into the top of the blender (flow approximately 0.3 cm wide at the top of the blender). Fibrids to Whatman International
Vacuum filtered over Limited # 41 filter paper and about 500
Excess DMAc was removed by washing five times with ml of water. The resulting fibrid cake was dried.

308 ml of a slurry of 0.3% solid fibrid and 0.616 g of 0.64 cm (0.24 cm)
A handsheet consisting of 60% PEI fibrids / 30% PPD-T flocks was prepared using 5 inch) flocs. Fibrids and flock and 2
Add 400 ml of water to British Pulp Eva
luation Apparatus) [Mavis Engineering Limited
eering, Ltd. ) No. 8233] and dispersing them for 5 minutes to produce a handsheet. This mass was added to the handsheet mold and additional water was added. The stock solution was stirred 10 times with a stir plate and then drained under vacuum through a screen (100 mesh screen) with a 0.15 mm diameter screen opening. The sample was laid between two ply (each side) blotters to remove excess moisture. The handsheet was then transferred to a blotter by quickly placing the sample and screen on the tabletop. The sample was dried on a handsheet hot plate dryer. The strength of the sample was determined to be sufficient for production on a fold linear paper machine.

Then, the hand sheet was hot-pressed at 6.895 MPa (1000 psi) and 279 ° C. (53
Pressed at 5 ° F) for 1 minute. Sample is 0.02N
/ M (0.86 lb / inch width) and 168 MPa
(24.43 kpsi).

The hand sheet formed in the same manner as in Example 1 was used.
Of fibrid (B) and PPD-T 0.64 cm
(0.25 inch) floc or MPD-I fibrids (C) and 0.64 cm (0.25 cm) of PPD-T.
Inches) made from flock.

[0050]

Table 7 breaking strength was normalized to N / m normalized (lbs / breaking strength / Modulus Modulus fibrids inches wide) basis weight, N / m MPa (kpsi) basis weight, MPa P EI fibrids 0.02 (0.86 ) 0.02 168 (24.43) 155 B 0.35 (20.02) 0.44 2862 (415.09) 3623 C 0.24 (13.65) 0.20 3481 (504.90) 2950 The breaking strength and modulus of all samples are 33.9.
"Normalize" to a reference weight of g / square inch (1.00 oz / square yard). As can be seen, B fibrids are superior to both A and C fibrid papers.

Example 7 A series of copolymers was prepared using IBC and an aromatic diamine Ar
(CH ₂ ) or a mixture of aromatic diamines. Each copolymer was prepared in a test tube equipped with a cap lined with polytetrafluoroethylene.
In each of the copolymer preparations, IBC (10.0
g, 28 mmol) and the appropriate diamine (s) (total 28 mmol, see table below) were kept in a test tube under nitrogen for 4 hours. The molten mixture was stirred during the early part of the reaction.

The aromatic diamine used to make the copolymer was the following diamine: metaphenylenediamine (MPD), where Ar = 1,3-phenylene, paraphenylenediamine (PPD), where Ar = 1 , 4-phenylene, 2,4-diaminotoluene (DAT), where Ar = 1-methyl-2,4-phenylene, 4,4′-
Diaminodiphenyl sulfone (DDS), where Ar =
4,4′-sulfonyldiphenylene, 3,4′-oxydiphenylamine (3,4′-ODA), where Ar =
3,4'-oxydiphenylene and 4,4'-sulfonyldiphenylamine (4,4'-ODA), where Ar = 4,4'-sulfonyldiphenylene.

The bis (lactam) monomer used in preparing the copolymer was N, N'-isophthaloylbis (caprolactam) (IBC). The copolymers evaluated were as follows:

[0054]

[Table 8] Items Polymer diamine mole A DAT / MPD-IBC 8.4 / 19.6 B DDS-IBC 28 C MPD-IBC 28 D 4,4 'ODA / DAT-IBC 19.6 / 8.4 E DAT-IBC 28 F 3,4 'ODA / MPD-IBC 8.4 / 19.6 G 4,4' ODA / DDS-IBC 19.6 / 8.4 H 4,4 'ODA-IBC 28 I 4,4' ODA / PPD-IBC 19.6 / 8.4 In an appropriate amount of solvent Prepare a 12% polymer solution by dissolving each of the above copolymers, the solvent is 100% DMAc for items A, B, E, F and I, but for items C, D, G and H 4% LiC
DMAc containing l. A pale brown / gold solution was obtained, which was filtered through glass wool.
The solution was heated to 85C.

The Waring 7011 blender is 50 m
DMAc (4% LiCl) and 200 ml distilled water. Using a blender operating at high speed, slowly pour 75 ml of the polymer solution into the top of the blender and the flow is 0.32 at the top of the blender.
cm (1/8 inch) wide. Each sample of fibrids (fibrids A-I) was vacuum filtered and approximately 500
Excess DMAc was removed by washing five times with ml of water. The resulting fibrid cake was dried.

The cake of each fibrid was mixed with an appropriate amount of water to produce a 1.2% solids slurry. This slurry was dispersed for 5 minutes as described in Example 2. 75
0 ml of this fibrid slurry was added to 2250 ml of water to produce a 0.3% solid slurry. 0.
A slurry of 3% fibrids was added at high speed in a Waring commercial blender (CB-6, type 33BL12) for 30 minutes.
"Scouring" for seconds.

An additional sample using MPD-I fibrids (item J) was processed for the same slurry preparation and scouring steps.

683 ml of a slurry of 0.3% solid fibrid and 1.1052 g of 0.32 cm (0.
125 inches) using a PPD-T floc
Handsheets were made of flocs of 0% fibrids A to I / 30% PPD-T. Add fibrids and flocs and an additional 2000 ml of water to the British
Pulp Evolution Apparatus (Britis)
h Pulp Evaluation Apparat
us) [Mavis Engineering Limited (M
avis Engineering, Ltd. ) No.
8233] and dispersing them for 5 minutes to produce a handsheet. This mass was added to the handsheet mold and additional water was added. The stock solution was stirred 10 times with a stir plate and then evacuated through a screen with a 0.15 mm diameter screen opening. The sample was laid between two ply (each side) blotters to remove excess moisture. The handsheet was then transferred to a blotter by quickly placing the sample and screen on the tabletop. Samples were prepared using the slurry of MPD-I fibrids described above as a control (item J). All handsheets were determined to be strong enough to be manufactured on a fold linear paper machine.

Next, the hand sheet was hot-pressed at 6.895 MPa (1000 psi) and 280 ° C. (53 ° C.).
Pressed at 5 ° F) for 1 minute.

The breaking strength and modulus values of these papers and of papers relatively made using MPD-I fibrids are described below.

[0061]

[Table 9] Normalized breaking strength, N / m Normalized breaking strength Modulus, modulus, item (lb / inch width) (lb / inch width) MPa (kpsi) MPa (kpsi) A 0.35 (19.93) 0.82 (47.18) 1331 (193.06) 3151 (457.05) B 0.20 (11.62) 0.33 (18.73) 1815 (263.27) 2926 (424.36) C 0.44 (25.44) 0.67 (38.54) 1672 (242.50) 2532 (367.37) D 0.56 (32.37) ) 0.80 (45.64) 2288 (331.86) 3236 (467.87) E 0.24 (14.02) 0.34 (19.65) 975 (141.47) 1367 (198.30) F 0.50 (28.86) 0.59 (34.11) 1858 (269.51) 2197 (318.57) G 0.44 ( 25.77) 0.48 (27.32) 2068 (299.98) 2236 (324.30) H 0.42 (24.21) 0.37 (21.04) 2265 (328.50) 1969 (285.53) I 0.70 (40.07) 0.55 (31.40) 2469 (358.02) 1935 (280.58) J 0.25 (14.48) 0.21 (12.30) 1528 (221.61) 1298 (188.28) The breaking strength and modulus of all samples are "normalized" to the same reference weight as the control in item J. As understood from these data, items A to I are superior to item J.

Example 8 N, N'-isophthaloylbis (caprolactam) and
And 3,4'-oxydiphenylamine
US Patent Application Serial No. 07 / 402,295
Reaction together in the order
A rimer was formed: [O = Cm-phenylene-C = O]_0.91  [HN-3,4'-oxydiphenylene-N
H]_0.91And [O = C- (CH_Two)_Four-NH]_0.09  About 50 pounds of this polymer (0.5-0.6 inherent viscosity)
To produce a 30% solids solution
Dissolved in enough DMAc (4% LiCl). this
A 30% solids solution is prepared in US Pat. No. 3,018,091.
In a fibrillator of the type described in Living
Washing the fibrids with water, DMAc and chloride
Of about 1.0%, respectively, based on the polymer
And 0.3%. The resulting fibrid case
The cake did not dry.

The cake of fibrids was mixed with an appropriate amount of water to produce a 1.2% solids slurry. This slurry was dispersed for 5 minutes as described in Example 2 above.
750 ml of this fibrid slurry was added.
A slurry of 0.3% fibrids was scoured at high speed for 30 seconds in a Waring blender (CB-6, 33BL12).

MPD-I fibrids (see, Example 7,
An additional sample using item J) was processed for the same slurry preparation and scouring steps.

683 ml of a slurry of 0.3% solid fibrid and 1.1052 g of 0.32 cm (0.
125 inches) using a PPD-T floc
Handsheets were made of flocs of 0% fibrids A to I / 30% PPD-T. Add fibrids and flocs and an additional 2000 ml of water to the British
Pulp Evolution Apparatus (Britis)
h Pulp Evaluation Apparat
us) [Mavis Engineering Limited (M
avis Engineering, Ltd. ) No.
8233] and dispersing them for 5 minutes to produce a handsheet. This mass was added to the handsheet mold and additional water was added. The stock solution was agitated 10 times with a stir plate and then evacuated through a 100 mesh screen. The sample was laid between two ply (each side) blotters to remove excess moisture. The handsheet was then transferred to a blotter by quickly placing the sample and a 100 mesh screen on the table top. A sample was prepared using the slurry of MPD-I fibrids described above as a control (Example 7, item J). All handsheets were determined to be strong enough to be manufactured on a fold linear paper machine.

Then, the hand sheet was hot-pressed at 6.895 MPa (1000 psi) and 280 ° C. (53
Pressed at 5 ° F) for 1 minute.

The breaking strength and modulus values of these papers and of the papers relatively made using MPD-I fibrids are described below.

[0068]

[Table 10] Normalized breaking strength, N / m Normalized breaking strength Modulus, modulus, item (lb / inch width) (lb / inch width) MPa (kpsi) MPa (kpsi) A 0.41 (23.62) 0.87 (49.73) 1201 (174.27) 2530 (366.88) B 0.25 (14.48) 0.21 (12.30) 1528 (221.61) 1298 (188.28) Breaking strength and modulus are normalized to the same reference weight as the control in item J. " As understood from these data, item A is superior to item J. The main features and aspects of the present invention are as follows.

1, 90 to 10% by weight of the following units:

[0070]

Embedded image

Wherein n is 4 or 5, and X is 0.0
1 to 0.50, and Ar is 3,4′-oxydiphenylene, 4,4′-oxydiphenylene, 4,4 ′
-Sulfonyldiphenylene, 1,3-phenylene, 1-
Methyl-2,4-phenylene and a group selected from a mixture of such groups or a mixture of up to 50 mol% of 1,4-phenylene groups based on a mixture of such groups with groups, A high strength sheet structure consisting essentially of floc of 10-90% by weight carbon fiber, aramid fiber or glass fiber held in place by essentially composed fused fibrids.

2. The first method using carbon flocs.
Item 7. The sheet structure according to item 1.

3. The seat structure according to the above item 1, wherein an aramid floc is used.

4. The sheet structure according to the above item 1, wherein a glass floc is used.

5. The sheet structure according to the above item 1, wherein X is from 0.03 to 0.30.

6. Fibrids have the following units:

[0077]

Embedded image

The sheet structure according to claim 1, wherein X is from 0.01 to 0.50.

7. Fibrids have the following units:

[0080]

Embedded image

The sheet structure according to claim 1, wherein X is from 0.01 to 0.50.

8. Fibrids have the following units:

[0083]

Embedded image

Wherein Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene groups and X is from 0.01 to 0.50, consisting essentially of
Item 2. The sheet structure according to Item 1.

9. The following units:

[0086]

Embedded image

Wherein n is 4 or 5, and X is 0.0
1 to 0.50, and Ar is 3,4′-oxydiphenylene, 4,4′-oxydiphenylene, 4,4 ′
-Sulfonyldiphenylene, 1,3-phenylene, 1-
Methyl-2,4-phenylene and a group selected from a mixture of such groups or a mixture of up to 50 mol% of 1,4-phenylene groups based on a mixture of such groups with groups, A fused fibrid consisting essentially of:

10. The fibrid according to the above item 9, wherein X is 0.03 to 0.30.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hamid Moaied Gorasi 23112 Mid, Virginia, USA Lodian Walkers Valley Road 3507 (56) Reference European Patent Application Publication 366316 (EP, A) (58) Fields Investigated (Int.Cl. ⁶ , DB name) D21H 5 / 18,5 / 20

Claims (2)

(57) [Claims] 1 to 90% by weight of the following units: Wherein n is 4 or 5, X is 0.01 to 0.50, and Ar is 3,4'-
Oxydiphenylene, 4,4′-oxydiphenylene,
4,4'-sulfonyldiphenylene, 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such groups or up to 50 mol% based on such mixtures of groups. From a mixture of 10-90% by weight floc of carbon, aramid or glass fibers held in place with fused fibrids consisting essentially of a mixture selected from a mixture with 1,4-phenylene groups. High strength sheet structure. 2. The following unit: Wherein n is 4 or 5, X is 0.01 to 0.50, and Ar is 3,4 ′
-Oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-sulfonyldiphenylene, 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such groups or such A fused fibrid consisting essentially of a group selected from a mixture of up to 50 mol% of 1,4-phenylene groups, based on the mixture of groups.