Translucent fibre composite materials comprising chemically modified polymers

Abstract

The present invention relates to a fibre composite material W of increased translucency and/or mechanical strength, comprising a copolymer C encompassing monomers A-1, where A-1 form covalent bonds with functional groups B-1 on the surface of fibres B embedded in the fibre composite material W, and this fibre composite material W has greater translucency and/or mechanical strength than a fibre composite material Win which the copolymer C contains no A-1. The present invention further embraces a method for producing a fibre composite material W of increased translucency and/or mechanical strength.

Claims

1. A fiber composite material W consisting of: (A) 20-99.5 wt % of a polymer matrix in the form of a thermoplastic polymer composition A comprising: (A1) at least one copolymer C comprising monomers A-I and monomers A-II and optionally further monomers; (A2) optionally one or more dyes F; and (A3) optionally one or more assistants H; and (B) 0.5-80 wt % of fibers B whose surface displays functional groups B-I which form a covalent bond with said monomers A-I, but not with said monomers A-II, (C) 0-79.5 wt % of polymer D, and (D) optionally one or more adhesion promoters, wherein optionally the light transmission through said fiber composite material W is not less than 10% higher than with a comparable fiber composite material that is the same as the fiber composite material W except that monomers A-II fully replace said monomers A-I, and wherein the flexural strength of said fiber composite material W is not less than 20% higher than with a comparable fiber composite material that is the same as the fiber composite material W except that monomers A-II fully replace said monomers A-I.

2. The fiber composite material W as claimed in claim 1 wherein said copolymer C has a construction comprising not less than 0.1 wt of monomers A-I.

3. The fiber composite material W as claimed in claim 1 wherein said thermoplastic polymer composition A comprises 90-99.5 wt % of said copolymer C.

4. The fiber composite material W as claimed in claim 1 wherein said monomers A-I are selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM), tert-butyl (meth)acrylate, and glycidyl (meth)acrylate (GM).

5. The fiber composite material W as claimed in claim 1 wherein said copolymer C is a styrene copolymer C comprising styrene (S) as monomers A-II.

6. The fiber composite material W as claimed in claim 1 wherein said functional groups B-I at the surface of said fibers B are selected from the group consisting of hydroxyl groups, ester groups, and amino groups.

7. The fiber composite material W as claimed in claim 1 wherein said fibers B embed into said fiber composite material W layerwise.

8. The fiber composite material W as claimed in claim 1 wherein: (A) said polymer matrix A comprises not less than 75 wt % of styrene copolymer C, maleic anhydride (MA) as monomers A-I, styrene (S) as monomers A-II; and (B) said fibers B are glass fibers displaying hydroxyl groups in the form of silanol groups as functional groups B-I on the surface, wherein the MA moieties are at least partly esterified with the silanol groups on the surface of said fibers B.

9. The fiber composite material W as claimed in claim 1 wherein the light transmission through said fiber composite material W is not less than 15% higher than with a comparable fiber composite material that is the same as the fiber composite material W except that monomers A-II fully replace said monomers A-I.

10. The fiber composite material W as claimed in claim 1 wherein the flexural strength of said fiber composite material W is not less than 50% higher than with a comparable fiber composite material that is the same as the fiber composite material W except that monomers A-II fully replace said monomers A-I.

11. The fiber composite material W as claimed in claim 1 wherein no adhesion promoter from the group consisting of aminosilanes and epoxy compounds was used in the production of said fiber composite material W.

12. A fiber composite material W obtained by a method comprising the steps of: (i) providing: (A) 20-99.5 wt % of a polymer matrix in the form of a thermoplastic polymer composition A comprising: (A1) at least one copolymer C comprising monomers A-I and monomers A-II and optionally further monomers; (A2) optionally one or more dyes F; and (A3) optionally one or more assistants H; and (B) 0.5-80 wt % of fibers B whose surface displays functional groups B-I which are capable of forming a covalent bond with said monomers A-I, but not with said monomers A-II; (C) 0-79.5 wt % of polymer D, and (D) optionally one or more adhesion promoters, (ii) melting said thermoplastic polymer composition A and contacting same with said fibers B from step (i); and (iii) reacting at least some of said monomers A-I of said copolymer C and at least some of said functional groups B-I of said fibers B from step (ii) to form covalent bonds, wherein optionally the light transmission through said obtained fiber composite material W is not less than 10% higher than with a comparable fiber composite material that is the same as the fiber composite material W except that monomers A-II fully replace said monomers A-I, and wherein the flexural strength of said fiber composite material W is not less than 20% higher than with a comparable fiber composite material that is the same as the fiber composite material W except that monomers A-II fully replace said monomers A-I.

13. The fiber composite material W as claimed in claim 1 wherein said fibers B are embed layerwise as wovens into said fiber composite material W and wherein no adhesion promoter from the group consisting of aminosilanes and epoxy compounds was used in the production of said fiber composite material W.

Description

FIGURES

(1) FIG. 1 shows the fiber composite materials W obtained by test #1. FIG. 1A depicts the visual documentation. FIG. 1B shows the microscopic view of a section through the horizontally disposed laminar fiber composite material W (at left: 25 fold magnification, at right: 50 fold magnification), wherein the fibers are clearly recognizable as a horizontally extending dark layer between the light-colored layers of thermoplastic molding composition. FIG. 1C shows the 200 fold magnification, which reveals that the impregnation is incomplete in some places.

(2) FIG. 2 shows the fiber composite materials W obtained by test #2. FIG. 2A depicts the visual documentation. FIG. 2B shows the microscopic view of a section through the horizontally disposed laminar fiber composite material W (at left: 25 fold magnification, at right: 50 fold magnification), wherein the fibers are clearly recognizable as extending dark layer between the light-colored layers of thermoplastic molding composition. FIG. 2C shows the 200 fold magnification, which reveals that the impregnation is partly incomplete.

(3) FIG. 3 shows the fiber composite materials W obtained by test #3. FIG. 3A depicts the visual documentation. FIG. 3B shows the microscopic view of a section through the horizontally disposed laminar fiber composite material W (at left: 25 fold magnification, at right: 50 fold magnification), wherein no layer of fibers is recognizable. FIG. 3C shows the 200 fold magnification, which reveals that the impregnation is substantially complete.

(4) FIG. 4 shows the fiber composite materials W obtained by test #4. FIG. 4A depicts the visual documentation. FIG. 4B shows the microscopic view of a section through the horizontally disposed laminar fiber composite material W (at left: 25 fold magnification, at right: 50 fold magnification), wherein no layer of fibers is recognizable. FIG. 4C shows the 200 fold magnification, which reveals that the impregnation is not fully complete in some places.

(5) FIG. 5 shows the fiber composite materials W obtained by test #5. FIG. 5A depicts the visual documentation. FIG. 5B shows the microscopic view of a section through the horizontally disposed laminar fiber composite material W (at left: 25 fold magnification, at right: 50 fold magnification), wherein no layer of fibers is recognizable. FIG. 5C shows the 200 fold magnification, which reveals that the impregnation is not fully complete in few places.

(6) FIG. 6 shows the production of fiber composite materials W (here: woven glass fiber fabrics) in the V25-V28 press inlet. It is clearly apparent that such a production method allows continuous manufacture. What is more, the embossed pattern reveals that said fiber composite material W is also three-dimensionally formable.

(7) FIG. 7 shows schematically the genesis of the unwanted formation of surface waves (texture).

EXAMPLES

(8) Process Parameters:

(9) Tests were carried out on an interval hot press capable of producing a fiber/sheet composite from polymer sheet, melt or powder, for the quasi-continuous production of fiber-reinforced thermoplastic semi-finished products, laminates and sandwich plates.

(10) Plate width: 660 mm

(11) Laminate thickness: 0.2 to 9.0 mm

(12) Laminate tolerances: max. ±0.1 mm, similar for semi-finished product

(13) Sandwich plate thickness: max. 30 mm

(14) Output: about 0.1-60 m/h, depending on quality and component part thickness

(15) Nominal speed of advance: 5 m/h

(16) Mold pressure: press unit 5-25 bar, continuously adjustable (optional) for minimum and

(17) maximum tool size

(18) Mold temperature regulation: 3 heating and 2 cooling zones

(19) Mold temperature: up to 400° C.

(20) Mold length: 1000 mm

(21) Press opening stroke: 0.5 to 200 mm

(22) Manufacturing direction: right to left

(23) Technical data of melt plastication:

(24) Batchwise melt application in midply for production of fiber-reinforced thermoplastic

(25) semi-finished products

(26) Screw diameter: 35 mm

(27) Max. swept volume: 192 cm.sup.3

(28) Max. screw speed: 350 rpm

(29) Max. output stream: 108 cm.sup.3/s

(30) Max. output pressure: 2406 bar specific

(31) Transparency was measured on 1 mm organopanel samples in % of white daylight (100%) using a transparency-measuring instrument Byk Haze gard i (BYK-gardner, USA) as per ASTM D 1003 (such as ASTM D 1003-13).

(32) Applied Thermoplastic Combinations A: A1 (comparative): S/AN with 75% styrene (S) and 25% acrylonitrile (AN), viscosity number 60, Mw 250 000 g/mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene calibration standards) A2: S/AN/maleic anhydride copolymer having the composition (wt %): 74/25/1, Mw 250 000 g/mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene calibration standards) A3: mixture of A2:A1=2:1 A4: mixture of A2:A1=1:2

(33) Employed Fiber Textiles B: B1: Bidirectional glass fiber noncrimp fabric 0/90° (GF-GE) of basis weight=590 g/m.sup.2, weft+warp=1200 tex [e.g., KN G 590.1 from P-D Glasseiden GmbH] B2: 2/2 twill glass fiber weave (GF-KG) of basis weight=576 g/m.sup.2, weft+warp=1200 tex

(34) The combination and parameter settings employed in connection with tests #1-5 are listed in the table which follows:

(35) TABLE-US-00001 TABLE 1 Production conditions for fiber composite materials W Molding Pressing Temperature pressure time Thickness Test # Composite* profile (bar) (s) (mm) 1 A1 + B1 220-240-260-160-80 20 20 1 (comp.) 2 A1 + B1 220-280-300-160-80 25 30 1 (comp.) 3 A2 + B1 240-300-320-160-80 20 20 1 4 A3 + B1 240-300-320-160-80 20 30 1 5 A4 + B1 240-300-320-160-80 20 30 1 *Components A + B1: 0.465 mm thickness textile construction, 0.653 mm thickness matrix construction, total volume matrix: 22 ml, fiber volume fraction: 41.6%, overall density of semi-finished product: 1.669 g/ml, overall thickness of semi-finished product: 1.117 mm

(36) Test #1 (Comparative Test)

(37) The results are shown in FIG. 1.

(38) Visual assessment at the surface of the semi-finished product:

(39) Macroimpregnation: complete

(40) Microimpregnation: clearly incomplete

(41) Microscopic assessment in interior of semi-finished product:

(42) Matrix layer in midply: clearly recognizable

(43) Matrix layer in topply: not recognizable by roving

(44) Impregnation of warp threads: unimpregnated regions in the center, slightly impregnated peripherally

(45) Impregnation of weft threads: distinctly unimpregnated regions in the center, slightly impregnated peripherally

(46) Air inclusions: minimally and only in the roving

(47) Consolidation: insufficient, damage to warp and weft threads

(48) Test #2

(49) The results are shown in FIG. 2.

(50) Visual assessment at the surface of the semi-finished product:

(51) Macroimpregnation: complete

(52) Microimpregnation: incomplete in several places

(53) Microscopic assessment in interior of semi-finished product:

(54) Matrix layer in midply: recognizable

(55) Matrix layer in topply: minimally recognizable by roving

(56) Impregnation of warp threads: unimpregnated regions recognizable in the center, partly impregnated peripherally, partly unimpregnated

(57) Impregnation of weft threads: unimpregnated regions in the center, slightly impregnated peripherally

(58) Air inclusions: minimal

(59) Consolidation: inadequate, distinct damage to weft threads

(60) Test #3

(61) The results are shown in FIG. 3.

(62) Visual assessment at the surface of the semi-finished product:

(63) Macroimpregnation: complete

(64) Microimpregnation: complete

(65) Test #3, Microscopic assessment in interior of semi-finished product:

(66) Matrix layer in midply: not recognizable

(67) Matrix layer in topply: readily recognizable

(68) Impregnation of warp threads: unimpregnated regions scarcely recognizable, efficiently impregnated peripherally

(69) Impregnation of weft threads: unimpregnated regions scarcely recognizable, efficiently impregnated peripherally

(70) Air inclusions: very many, large blisters recognizable

(71) Consolidation: good, no damage

(72) Test #4

(73) The results are shown in FIG. 4.

(74) Visual assessment at the surface of the semi-finished product:

(75) Macroimpregnation: complete

(76) Microimpregnation: predominantly complete

(77) Microscopic assessment in interior of semi-finished product:

(78) Matrix layer in midply: scarcely recognizable

(79) Matrix layer in topply: recognizable

(80) Impregnation of warp threads: unimpregnated regions scarcely recognizable, efficiently impregnated peripherally

(81) Impregnation of weft threads: unimpregnated regions recognizable, but impregnated peripherally

(82) Air inclusions: none recognizable

(83) Consolidation: satisfactory, central damage recognizable for weft threads

(84) Test #5

(85) The results are shown in FIG. 5.

(86) Visual assessment at the surface of the semi-finished product:

(87) Macroimpregnation: complete

(88) Microimpregnation: predominantly complete

(89) Microscopic assessment in interior of semi-finished product:

(90) Matrix layer in midply: not recognizable

(91) Matrix layer in topply: recognizable

(92) Impregnation of warp threads: not many unimpregnated regions recognizable, efficiently impregnated peripherally

(93) Impregnation of weft threads: not many unimpregnated regions recognizable, efficiently impregnated peripherally

(94) Air inclusions: none recognizable

(95) Consolidation: partly good, partly insufficient, local damage recognizable for weft threads

(96) Summary of Test Results

(97) TABLE-US-00002 TABLE 2 Summary of tests and assessment Maleic Max. anhydride tempera- Trans- concentration ture Impregnation** parency Consol- Test # Composite* (wt %) (° C.) Macro Micro (%) idation** 1 (comp.) A1 + B1 0 260 1 5 1 5 2 (comp.) A1 + B1 0 300 1 4 3 4 3 A2 + B1 1 320 1 1 40 2 4 A3 + B1 0.66 320 1 2 25 3 5 A4 + B1 0.33 320 1 2 20 4 *Components A + B1: 0.465 mm thickness textile construction, 0.653 mm thickness matrix construction, total volume matrix: 22 ml, fiber volume fraction: 41.6%, overall density of semi-finished product: 1.669 g/ml, overall thickness of semi-finished product: 1.117 mm **1 = perfect, 2 = good, 3 = partial, 4 = minimal, 5 = bad/none

(98) TABLE-US-00003 TABLE 3 Visual and tactile comparison of invention settings/formulations with conventional organopanels Maleic Print- anhydride ability with Trans- concentration Surface 45 mdyne parency Test # Composite (wt %) finish* ink** (%) 1 A1 + B1 0 2 1 1 (comp.) 2 A1 + B1 0 2 1 3 (comp.) 3 A2 + B1 1 1-2 1 40 4 A3 + B1 0.66 1-2 1 25 5 A4 + B1 0.33 1-2 1 20 6 Bond laminates 0 4-5 1 0 composite from ca. 60% glass fiber weave and 40% polyamide 7 Composite from ca. 0 4-5 5 0 60% glass fiber weave and 40% polypropylene *1 = completely smooth, 2 = substantially smooth, 3 = slighty rough, 4 = moderately rough, 5 = fibers are distinctly noticeable to the touch **1 = perfect, 2 = good, 3 = partial, 4 = minimal, 5 = bad/none

(99) Test #6

(100) The results are shown in Table 5. The combinations and parameter settings used in connection with test #6 are listed in the table which follows:

(101) TABLE-US-00004 TABLE 4 Production conditions for fiber composite materials W Molding Pressing Temperature pressure time Thickness Test # Composite* profile (bar) (s) (mm) 4 A1 + B1 220-240-300-160-80 20 20 1 12 A3 + B1 220-240-300-160-80 20 20 1 28 A1 + B2 240-300-320-160-80 20 20 1 26 A3 + B2 240-300-320-160-80 20 30 1 *Components A + B1: 0.465 mm thickness textile construction, 0.653 mm thickness matrix construction, total volume matrix: 22 ml, fiber volume fraction: 41.6%, overall density of semi-finished product: 1.669 g/ml, overall thickness of semi-finished product: 1.117 mm

(102) TABLE-US-00005 TABLE 5 Comparison of flexural strength. Delta Delta Test # 8 9 (%) 10 11 (%) Reinforcement NCF (B1), warp 2/2 twill direction weave (B2) Matrix A1 A3 A1 A3 Bending test: Modulus (GPa) 19.7 22.5 14 21.1 19.6 −7 Breaking 211 462 119 423 528 25 stress (MPa)

(103) Table 5 shows the fiber composite materials W obtained in a test series. In each case, a purely SAN copolymer (A1) and an S/AN/maleic anhydride copolymer (A2) were combined with a commercially available noncrimp and woven fabric reinforcement in an identical process and tested. The fiber volume content of the composites was 42%. The improved quality of impregnation and bonding between fiber and matrix shows itself not in the flexural stiffness, but significantly in the flexural strength (breaking stress) of the samples tested.

(104) Test #7

(105) The results are shown in Table 6.

(106) TABLE-US-00006 TABLE 6 Comparison of total waviness profile height Wt. Test # 12 13 14 Reinforcement fiber (B3) Matrix (A4) SAN PC PA6 OD mean Wt (μm) 5.2 11.7 12.3 maximum Wt (μm)) 7.8 22.3 17.2

(107) The components involved here are defined as follows: SAN: SAN-MA terpolymer, weight composition (wt %): 73/25/2, Mw: 250 000 g/mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene standards), MVR: 15-25 cm.sup.3/10 min at 220° C./10 kg (ISO1133), viscosity number (in DMF) J=61-67 ml/g PC OD: easy flowing, amorphous polycarbonate of optical grade for optical disks PA6: partly crystalline, easy flowing nylon-6 Fibers (B3): 2/2 twill glass fiber weave (GF-KG) of basis weight=300 g/m.sup.2, weft+warp=320tex

(108) As is clear from Table 6, the use of SAN-MA terpolymer is particularly advantageous to obtain a low level of total waviness profile height on the surface. PC OD proved sensitive to stress cracking.

Examples of Multilayer Organopanels

(109) The fiber composite materials described (organopanels), especially those comprising an amorphous, thermoplastic matrix, are very useful for producing transparent and translucent moldings, sheets and coatings. Some examples are shown hereinafter. Unless otherwise stated, the shaped articles are produced in injection molding processes.

Example 1

Production of Fiber Composite Material M

(110) 40 wt %, based on the fiber composite material of an acrylonitrile-styrene maleic anhydride copolymer in the form of a thermoplastic molding composition A (prepared from: 75 wt % of styrene, 24 wt % of acrylonitrile and 1 wt % of maleic anhydride) is compounded with 60 wt %, based on the fiber composite material, of a glass-based reinforcing fiber having chemically reactive functionality (silane groups) at the surface [GW 123-580K2 from P-D Glasseiden GmbH].

Example 2

Production of Fiber Composite Material N

(111) 65 wt %, based on the fiber composite material of an acrylonitrile-butadiene-styrene copolymer in the form of a thermoplastic molding composition A (ABS prepared from: 45 wt % of butadiene, 30 wt % of styrene, 24 wt % of acrylonitrile and 1 wt % of maleic anhydride) is compounded with 35 wt %, based on the fiber composite material of a glass-based reinforcing fiber having chemically reactive functionality (silane groups) at the surface [GW 123-580K2 from P-D Glasseiden GmbH]. The fiber composite material is subsequently subjected to ribbing.

Example 3

Production of Shaped Articles from Fiber Composite Materials M and N

Example A: Washing Machine Windows

Example B: Lens Covers

(112) Enhanced stiffness is observed for the window and the lens cover versus corresponding materials consisting of glass. The organopanels are further less sensitive to scratches and pressure.

(113) Further Bending Stress Tests on Fabric-Reinforced Fiber Composite Materials

(114) The components are as defined above. The bending stress and the flexural modulus were determined to DIN 14125:2011-05. The combinations and parameter settings of the method described in claim 1 are listed in the table which follows:

(115) TABLE-US-00007 TABLE 7 Compositions Comp. 1, Comp. 2, Comp. 10 and Comp. 15 and invention compositions V3 to V9 and V11 to V14. X: weight ratio of components A:B = 60:40 #. A1 A2 A3 A4 B1 B2 T [° C.] t [s] Comp. 1 X X 260 20-30 Comp. 2 X X 300 30-30 V3 X X 280 20-30 V4 X X 280 40 V5 X X 320 30-30 V6 X X 300 20-30 V7 X X 320 20-30 V8 X X 310 20-30 V9 X X 320 20-30 Comp. 10 X X 320 20-30 V11 X X 320 20-30 V12 X X 320 20-30 V13 X X 320 20-30 V14 X X 320 20-30 Comp. 15 X X 320 20-30

(116) The conditions under which the tests were carried out are reported in Table 7.

(117) The starting materials, the temperature and the pressing time were varied. The molding pressure was about 20 bar in all test series.

(118) TABLE-US-00008 TABLE 8 Mean maximal bending stress - warpways and weftways - of organopanels produced as per mixtures Comp. 2, V5, V7, V9, Comp. 10, V12 to V14 and Comp. 15, the production temperature being at least 300° C. in each case. Mean maximal bending #. Fiber direction stress [MPa] Comp. 2 warpways 211.23 weftways 184.94 V5 warpways 670.48 weftways 271.05 V7 warpways 590.98 weftways 301.21 V9 warpways 371.73 weftways 244.62 Comp. 10 warpways 319.8 weftways 236.01 V12 warpways 556.15 weftways 484.24 V13 warpways 528.96 weftways 386.83 V14 warpways 513.95 weftways 413.86 Comp. 15 warpways 423.03 weftways 301.40

(119) The means reported in Table 8 are computed from nine measurements each.

(120) Table 8 shows that the organopanels which are in accordance with the present invention—V5, V7, V9, V12, V13 and V14—have a higher mean maximal bending stress than the organopanels comprising a matrix containing 75 wt % of styrene (S) and 25 wt % of acrylonitrile (AN): Comp. 10 and Comp. 15. The comparison of V9 with Comp. 10 likewise shows that—under the same conditions (T=320° C. and t=30 s)—the organopanel of the present invention has a higher bending stress both warpways and weftways.

(121) It transpires that the method of producing the fiber composite material delivers improved products with a thermoplastic molding composition A, reinforcing fibers B.

(122) Further Investigation of Multilayered Fiber Composite Materials

(123) Technical data of interval hot press (IVHP):

(124) Quasi-continuous production of fiber-reinforced thermoplastic semi-finished products, laminates and sandwich plates

(125) Plate width: 660 mm

(126) Laminate thickness: 0.2 to 9.0 mm

(127) Laminate tolerances: max. ±0.1 mm, similar for semi-finished product

(128) Sandwich plate thickness: max. 30 mm

(129) Output: about 0.1-60 m/h, depending on quality and component part thickness

(130) Nominal speed of advance: 5 m/h

(131) Mold pressure: press unit 5-25 bar, continuously adjustable (optional) for minimum and maximum tool size

(132) Mold temperature regulation: 3 heating and 2 cooling zones

(133) Mold temperature: up to 400° C.

(134) Mold length: 1000 mm

(135) Press opening stroke: 0.5 to 200 mm

(136) Manufacturing direction: right to left

(137) Technical data of melt plastication:

(138) Batchwise melt application in midply for production of fiber-reinforced thermoplastic semi-finished products

(139) Screw diameter: 35 mm

(140) Max. swept volume: 192 cm.sup.3

(141) Max. screw speed: 350 rpm

(142) Max. output stream: 108 cm.sup.3/s

(143) Max. output pressure: 2406 bar specific herein:

(144) Melt volume: 22 ccm

(145) Isobaric=pressure-controlled molding process

(146) Isochoric=volume-controlled molding process

(147) T [° C.]=temperature of temperature zones* (*The press has 3 heating and 2 cooling zones. Reported in manufacturing direction)

(148) p [bar]=molding pressure per cycle: isochoric 20

(149) s [mm]=pressed thickness path limitation: 1.1 mm Temperature profile: (i) 210 to 245° C., hence about 220° C. (ii) 300 to 325° C., hence about 300° C. (iii) 270 to 320° C., hence about 280 to 320° C. (iv) 160 to 180° C. (v) 80° C.

(150) t[sec]=pressing time per cycle: 20-30 s

(151) Construction/lamination: 6-ply construction with melt midlayer; production method: melt direct (SD)

(152) Matrix components A:

(153) M1 (SAN type): styrene-acrylonitrile maleic anhydride (SAN-MA) terpolymer (S/AN/MA: 74/25/1) with an MA fraction of 1 wt % and an MVR of 22 cm.sup.3/10 min at 220° C./10 kg (measured to ISO1133);

(154) M1b corresponds to the aforementioned component M1 except that the matrix was additionally admixed with 2 wt % of carbon black.

(155) M2 (SAN type): styrene-acrylonitrile maleic anhydride (SAN-MA) terpolymer (S/AN/MA: 73/25/2.1) with an MA fraction of 2.1 wt % and an MVR of 22 cm.sup.3/10 min at 220° C./10 kg (measured to ISO1133);

(156) M2b corresponds to the aforementioned component M1 except that the matrix was additionally admixed with 2 wt % of carbon black.

(157) M3 (SAN type): Blend of 33 wt % M1 and 67 wt % of Luran VLN SAN copolymer, hence 0.33 wt % of maleic anhydride (MA) in the entire blend;

(158) M3b corresponds to the aforementioned component M3 except that the matrix was additionally admixed with 2 wt % of carbon black.

(159) PA6: partly crystalline, easy flowing Durethan B30S nylon

(160) PD(OD): easy flowing, amorphous polycarbonate of optical grade for optical disks;

(161) Fiber components B:

(162) Glass filament twill weave (codes: GF-KG(LR) or LR), twill construction 2/2, basis weight 290 g/m.sup.2, roving EC9 68tex, finish TF-970, delivered width 1000 mm (type: 01102 0800-1240; manufacturer: Hexcel, obtained from: Lange+Ritter)

(163) Glass filament twill weave (codes: GF-KG(PD) or PD), twill construction 2/2, basis weight 320 g/m.sup.2, roving 320tex, finish 350, delivered width 635 mm (type: EC14-320-350, manufacturer and supplier: PD Glasseide GmbH Oschatz)

(164) Glass filament noncrimp fabric (code: GF-GE(Sae) or Sae) 0°/45°/90°/−45°, basis weight 313 g/m.sup.2, main roving 300tex, finish PA size, delivered width 655 mm (type: X-E-PA-313-655, #7004344, manufacturer and supplier: Saertex GmbH&Co.KG)

(165) Sae n.s.=glass filament noncrimp fabric 300 g/m.sup.2, manufacturer's designation:

(166) Saertex new sizing, +45°/−45°/+45°/−45°

(167) Glass fiber web (code: GV50), basis weight 50 g/m.sup.2, fiber diameter 10 μm, delivered width 640 mm (type: Evalith S5030, manufacturer and supplier: Johns Manville Europe)

(168) Visual Assessment

(169) All the fiber composite materials produced are each obtainable as large-area flat organopanels in a continuous process, which were readily cuttable to size (into laminatable transportable dimensions such as, say, 1 m×0.6 m). In the transparent fiber composite materials, the embedded fiber material was just about recognizable on detailed inspection against the light. With the fiber composite materials having a (black) stained matrix, the embedded fiber material could barely be made out, if at all, even on closer visual inspection against the light.

(170) Microscopic Assessment

(171) Defects (voids, sink marks, etc.) were assessed via reflected light microscopy, while surface finish was assessed via confocal laser scanning microscopy (LSM). LSM was used to establish a plan view of a three-dimensional (3D) contour picture (7.2 mm×7.2 mm) of the local region measured and a two-dimensional (2D) representation of the height differences after scaling and applying various profile filters. Experimental errors and any general distortion/skewness of the sample were eliminated by the employment of profile filters (noise filter and tilt filter). The 2D height profile of the picture was transferred into line profiles, via defined measuring lines and through integrated software, and evaluated with computer support.

(172) The fiber composite materials produced each had four plies of the corresponding fabric of fibers (here GF-KG(PD)(4) or Sae(4)) embedded in the particular matrix. To further improve the comparability of the samples, a thin glass fiber web (GV50, see above) was applied to each of the fiber composite materials obtained, on both sides. This web had no significant influence on the mechanical properties.

(173) The mean total waviness profile height (mean Wt) and the arithmetical mean roughness value (Ra) were determined for numerous fiber composite materials. It transpired that mean Wt is distinctly <10 μm for all fiber composite materials wherein the matrix contains a functional component capable of reacting with the fibers, whereas it is distinctly <10 μm with fiber composite materials having comparable PA6 and PD(OD) matrices. The arithmetical mean roughness values determined were also distinctly lower for fiber composite materials that are in accordance with the present invention. The measured values below show this by way of example.

(174) TABLE-US-00009 TABLE 9 Measured results of LSM measurement with SAN matrix system - total waviness profile height (Wt) and arithmetical mean roughness value (Ra) Constitution +GF-KG(PD)(4) SAN(1) PC(1) PA6(1) Components M1b + PD M2 + PD M2b + PD M3b + PD PC(OD) + PD PA6 + PD mean Wt 7.141 7.187 5.181 5.425 11.745 12.323 mean Ra 3.995 4.415 4.17 3.451 6.406 4.968

(175) This became similarly clear on using a noncrimp fabric (such as Sae) instead of the woven fabric:

(176) TABLE-US-00010 TABLE 10 Measured results of LSM measurement with SAN matrix system − total waviness profile height (Wt) and arithmetical mean roughness value (Ra) Constitution +Sae(4) SAN(1) PA6(1) Components M1b + Sae M2b + Sae mean Wt 5.535 5.205 17.05 mean Ra 4.261 4.24 4.861

(177) Further tests were carried out to investigate the strength separately in the warp direction and in the weft direction. It was found that the fiber composite materials are very stable not only warpways but also weftways. Warpways the fiber composite materials are generally more stable than in the weft direction.

(178) Mechancal Properties

(179) Matrix Components A

(180) Matrix components A are as described above.

(181) Fiber Components B (Where not Described Above)

(182) FG290=woven glass filament fabric 290 g/m.sup.2, manufacturer's designation: Hexcel HexForce® 01202 1000 TF970

(183) FG320=woven glass filament fabric 320 g/m.sup.2, manufacturer's designation: PD Glasseide GmbH Oschatz EC14-320-350

(184) Sae=MuAx313, noncrimp glass filament fabric 300 g/m.sup.2, manufacturer's designation: Saertex X-E-PA-313-655

(185) Sae n.s.=noncrimp glass filament fabric 300 g/m.sup.2, manufacturer's designation: Saertex new sizing, +45°/−45°/+45°/−45°

(186) Number of layers (e.g., 4×=four layers of the particular fiber NCF or the particular fibers)

(187) The transparent fiber composite materials, into each of which a flat fibrous material was imported, were produced as follows. The fiber composite materials produced each had a thickness of about 1.1 mm. To further improve the comparability of the samples, a thin glass fiber web (GV50, see above) was applied to each of the fiber composite materials obtained, on both sides. This web has no significant influence on the mechanical properties or visual properties. The following flextural strengths to DIN EN ISO 14125 were determined for the samples:

(188) TABLE-US-00011 TABLE 11 Transparent fiber composite materials - flextural strength Glass Consti- content Thickness Elastic Flexural # tution [g/m.sup.2] Matrix [mm] modulus strength F/T_1 4xFG290 1260 M2 1.09 18.41 658.89 F/T_2 4xFG320 1380 M2 1.09 18.17 634.32 F/T_3 4xSae 1352 M2 1.16 18.44 444.33 F/T_4 Sae n.s. M2 1.17 15.93 621.04 F/T_5 4xFG320 1380 PC(OD) 1.14 23.36 377.97

(189) Also produced were the following black-stained fiber composite materials in each of which the matrix was admixed with 2 wt % of carbon black and into each of which flat fibrous material was imported. The fiber composite materials produced each had a thickness of about 1.1 mm. To further improve the comparability of the samples, a thin glass fiber web (GV50, see above) was applied to each of the fiber composite materials obtained, on both sides. This web has no significant influence on the mechanical properties or visual properties. The following flextural strengths to DIN EN ISO 14125 were determined for the samples:

(190) TABLE-US-00012 TABLE 12 Nontransparent fiber composite materials - flextural strength Glass Consti- content Thickness Elastic Flexural # tution [g/m.sup.2] Matrix [mm] modulus strength F/S_1 4xFG290 1260 M2 1.07 21.61 661.73 F/S_2 4xFG320 1380 M2 1.20 22.70 673.99 F/S_3 4xSae 1352 M2 1.15 14.92 385.21 F/S_4 4xSae 1352 PA6 1.13 14.30 477.77 F/S_5 4xFG320 1380 PA6 1.11 16.95 471.97

(191) It transpired, in summary, that the wovens used (FG290 and FG320) are processable into fiber composite materials having particularly high flexural strength. The fiber composite materials of the present invention, wherein the matrix contains a component (here: maleic anhydride (MA)) which reacts with the fibers, have a significantly higher flexural strength than the comparative molding compositions without such a component, such as PC(OD) or PA6.

(192) By contrast, Luran 378P G7 fiber composite material reinforced with chopped glass fibers, which is not in accordance with the present invention, merely gave a flextural strength of 150 MPa, hence a distinctly lower flexural strength.

(193) In addition, the fiber composite materials were tested for impact toughness and/or penetration resistance (Dart Test to ISO 6603). Again, the fiber composite materials exhibited a high stability of Fm >3000 N.

(194) Optional Further Processing

(195) It was also shown experimentally that the fiber composite materials obtained were readily formable into three-dimensional semi-finished products, for example into semi-finished half-shell products. It further transpired that the fiber composite materials obtained were printable and laminatable.

(196) Summary of Experimental Results

(197) The evaluation of different textile systems based on glass fiber with different matrix systems into a fiber composite material (organopanel) showed that good fiber composite materials are reproducibly obtainable (as organopanels and semi-finished products derived therefrom). These are obtainable in colored or colorless form. The fiber composite materials exhibited good to very good visual, tactile and mechanical properties (regarding their flexural strength and penetration resistance for example). Mechanically, the woven fabrics exhibited somewhat greater strength and stiffness than noncrimp fabrics. The styrene-copolymer-based matrices (SAN matrices) tended to lead to better fiber composite materials regarding mechanical characteristics than the alternative matrices such as PC and PA6. The fiber composite materials of the present invention were obtainable semi-automatically or fully automatically via a continuous process. The fiber composite materials (organopanels) of the present invention are three-dimensionally formable into semi-finished products in an efficient manner.