LU80332A1 - COMPOSITE MATERIAL ACRYLONITRILE-BUTADIENE-STYRENE-VINYLIDENE POLYFLUORIDE RESIN - Google Patents

Description

D. 50.129 Λ- *? T! 9 grand-dUCHÉ DE LUXEMBOURG Patent N "....... Q ..... Q ...... J ...... V“ du ..... 6 .QQfc.QbXe ..... l9.1.8 {fl®]} Mr. Minister cSSaeîrj of the National Economy and the Middle Classes

Title issued: ........................................

Industrial Property Department ^ £ 3y LUXEMBOURG

Patent Application I. Request ....... The company called: ..... CHEMICALS UGINE KUHLmNN, ..... TOUR .............. ...... (1) ....... MÂimmïLrJ ^. DEFE "SE ..... 2, ...... 5 _ * .......... to ..... 9.2.4" ............. ...............

....... COURBEVOIE, France, represented by Monsieur Jacques de ....................... @) ....... Muys. er, ..... aglÂsaafe ^ iLjgôâ ........................................ .................................................. .....

drops off _______ this ... six ... October ..... 19.0.0 ..... soixan.te-dix-.bw.lfc .________________________________________________ (3) at ........... 15 .________ ... hours, at the Ministry of National Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for an invention concerning: ________ '.'. Material ... ..composite ..... ré.s ± ne ..... açrYlQnltrll.erbutadld.nor.s.fcyrouer ....... (4) ............ r .éslne .... polyfluo.rur.e ..... de ..... γiny.lidèn.e ..!, .. * ............... .................................................. ................................................

declares, assuming responsibility for this declaration, that the inventor (s) is (are): ........ l. *. r ...... Gilb.er.fc. .... HÂSLE, ..... 4 .., ...... rU! E ..... Cb.ateaub.riand., ..... 1 ..... 6Qlô. o ..... HQ.SMT .: ON ...... (5) ......................... OISE.,. .....France............................................ .................................................. .................................................. .................................................. .............

........ 2. *. R .... Alb.er.fc ..... S.TRAS.SEL., ..... 3.Qj: ..... rue. ..Pasteur, ...... A ... 6..9.6.oq .... QU.LLINS ...... France ...

........ 3, .. r ..... Jac? ^ S .... V ^^ ffi., .... rue .... de ... la .... SQlifcali: e, .... Â .... 6o29.Q..îCïOff .... SM® .... | iOl, .... Fra ^ 2. the delegation of power, dated ..COURBEVOIE ......................... 2.9 ...... S.epfceilîbre. 197.8 3. description in language ........ Ir.aîl.Ç.aise ............................ ........ of the invention in two examples. : areas; 4 ...... /. / ............... ... drawing boards, in two copies; 5. the receipt of the fees paid to the Luxembourg Registration Office on ......... 6 ..... October ..... 19,7.8 ......... .................................................. .................................................. .................................................. ..................................................

k <hkhi / i / s / i / q / i / e / ^ hi4rh! Ù I $ khi ItikÀ / $ kéirM (£) / éa / (6) .............. .................................................. ................................ deposited in (7) .......... .................................................. .................................................. ..........................

the ................................................. .................................................. .................................................. .................................................. .................................................. ...................... (8) in the name of ...................... .................................................. .................................................. .................................................. .................................................. .......................... (9) elect domicile for him / her and, if appointed, for their proxy, in Luxembourg ... .....................................

, ........ 35, ..... bld. · ...... Royal ........................ .................................................. .................................................. .................................................. ............................... (io) „, requests the grant of a patent for the subject described and represented in the abovementioned appendices, - with postponement of this issue to ... ............ 1.8 ................... ....... months.

II. Deposit Minutes

The aforementioned patent application has been filed with the Ministry of National Economy and Middle Classes, Industrial Property Service in Luxembourg, on: ✓'tTV-î ..., V'x β .. ...... Pr. the Minister f- -: / A at 3 p.m. J if • Χ. 'Πΐ \ of the National Economy jet of the Middle Classes,' 7. i ................. * '/ Vis * V. / iß'

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! /. · A 68007 ’/; ·‘ .......... // / * v ... ..____ * ____ μ ____ _______! ... _____ ‘~. / / _____, ............. „.... 7“.

Λ 'D. 50.129 * Ψ * Brief Description filed in support of a request for

PATENT

at

Luxembourg

formed by: CHEMICALS UGINE KUHLMANN

for: "Composite material acrylonitrile-butadiene-styrene resin - polyvinylidene fluoride resin".

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I i! ”Composite material acrylonitrile-butadiene-styrene resin & ne - j: | 1 polyvinylidene fluoride resin ”; it: ί i; I ί I; Inventors:; i; ! Gilbert HA5LE, Albert STRASSEL and Jacques VANDOHE! 5; "Î’ ‘, ———, there! j it! ! :! : M '; ί! : i! 5; The subject of the present invention is a composite material! i i i; {| te consisting of an acrylonitrile-buiadiene-styrene terpolymer; i | not a word ! | commonly called ABS, coated with polyvinylidene fluoride, · •! 1 î ί it commonly known as PVF ~. According to the subject of the invention are cor- j I i: 2 j! | combined with PVFn organic or mineral fillers intended for; ! i I 2 1 Q; to screen with ultraviolet rays. Such a material has a j; ! resistance to chemical agents and mechanical properties after.

| :>: t · j aging, in particular impact resistance and elongation; j ί! i

If I; in traction, significantly higher than in ABS, i

! ; ! I

j! I The characteristics of this composite material are! IM i * 15 = even more unexpected than due to poor aging! i i i! '! i I ABS for bad weather or corrosive atmosphere it has been propc- 1 I - Λ | if so many protective coatings made of other polymers i'i ί! ! I res more resistant than ABS, such as acrylic, for example! it · i I | j polyvinyl chloride, polycarbonates. These means, far i

2CH to effectively protect AB5, have the disadvantage in J

j ij certain cases of harming their mechanical properties,; î i i! »F j | | j! The composite material which is the subject of the invention, including the element: i Ί! ’,; I _ j I] ment principal is in ABS is characterized in that at least on j j t! *} j i! one of the largest surfaces of the ABS element is fixed a re- ":; i i. 25 PV PVF.- garment, containing a mineral or organic filler;

Mi 2. ΐ: ·! cover against ultraviolet rays,! i; > ΐ! i? .1 PVF_ coating containing mineral filler or i

Mi 2 d j ij. organic is generally a maximum thickness ten times less! 1 M oue the thickness of the ABS element without however the thickness 30: of the coating is not more than 400 microns and preferably! ί: greater than 100 microns, j! . ; ; i i; :] This coating can be in the form of a film: l / Mi i „.2Ί t s» I; j

i! i J

ί! :; Μ or film prepared according to conventional methods. We can by j; j! Example mix the charge with PVF_ in solution in a solvent, j

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• ·· then coat on a transfer paper the mixture obtained in a j / '; j to obtain a film of desired thickness after evaporation of the solvent,. 5 i Suitable for the production of this coating polyfluo-i resin; vinylidene rure, it being understood that under this designation are (i · · i * j include pure PVF2 and copolymers containing at least 70> one!!!! weight of PVF-. j; j!. Inorganic or organic fillers are well known iji ^.., * h0; known to those skilled in the art. These are the products used i

1 »· I

! i 1 commonly used as anti-ultraviolet screen in therrnoplasti-.

! Yes ; not a word! ques. It can be mineral fillers such as for example; ! j! metal oxides or salts, or even metal powders; •; i such as zinc oxide, titanium oxide, silica, talc, le: 15; barium sulfate, calcium carbonate, silico-aluminates 1 day! powders of aluminum, copper, bronze. It can also be organic fillers, for example simple pigments ί 11 or commercial ultraviolet absorbing agents such as those in! ! I i 1

j j I X

j i | basa of benzophenones, benzotriazoles, substituted amines,:

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'20. · From salicy.lates. These charges can be used alone or e.n j 1 I; i i>; mixed. In general, the coating of PVF ^ may also contain! | ï weight of 0.1 to 50% of mineral filler and 0.1 to 10% of filler; ! ! I i j} organic, j! The ABS element suitable for making the material; ! . i 25! composite is classic. It can be prepared from the product: • f I ii! 'Obtained by polymerization of a mixture of an alkenic nitrile and J j ·' j =, 1. ji of a vinyl aromatic hydrocarbon, such as mé ~ |

l î i. ‘I

i !! acrylonitrile-styrene or alphamethylstyrene mixture, in the presence; he: . not a word ; ί of a polybutadiene, In general the terpolymer is prepared from; i; ] 3Q! ; from 5 to 40% by weight of acrylonitrile, 30 to 00% by weight of stvrc- ’

; I i

I i | ne and 10 to 60% by weight of polybutadiene, L-’ABS can contain 1 - ·! I î; all the usual additives to this type of resin as well as; i j | . *! i! ï pie: fillers, pigments, plasticizers, protective agents and so on! ij very «| 35 '! The composite material can be produced according to pro-j j i! ceded known to intimately adhere elements thermn- ‘» * i: /; 1 1 i, i! •, \ •! ! ; h s: plastics. An interesting manufacturing process, described in

* i! . I

; French patent application 77 / 09.917, consists of filing on the: * ii ·! j: surface to fix PVF? containing a filler, a thin film of polyurethane using a solution of polyurethane in one; 5:! aprotic polar solvent. The whole is heated to a temperature j | ! between-120 ° C and 300DC for a few minutes so as to: • il * J || remove the solvent. After cooling we apply the surface

! I

; I; treated with PVF ~ containing a charge on the ABS element and on; ί ^ u; *. \,; ♦; adheres the assembly by heat sealing, i; î.

* □ ’! Due to the special characteristics of this material; j i! ; i i; composite riau, in particular its impact resistance and its allcn- I I j j gement in traction after aging whose values can; l.

ï sometimes reaching twice that of the element only in l; | {| ABS aged under the same conditions, it is possible to use it; ! | j r] 5î; used for the manufacture of products requiring good performance * ·. j j aging. Its use is envisaged for the manufacture, for example, of hulls of boats, of bodywork elements.

Ij of vehicles, internal fittings of refrigerators or cupboards—! . ? I’m refrigerated, in building facade panels, 20d | The following examples illustrate the invention j i -: J The aging of the composite material is accelerated; | to control its mechanical properties, using a device! i -reil Xénotest 450, The samples are kept at around 25 ° C; || ! for at least 1 GB hours in an air atmosphere with a relative humidity j? 5 of 65 5'a with water spraying lasting 5 minutes! i, every 30 minutes. This test corresponds to procedure j! test defined by the manufacturer of the Xenotest 450, As an indication! . | j ij catif, it is estimated that to have the equivalence with an exposure j i i ^ j i j; outdoors in temperate climates, durations at. Xenotest 450 rioi-

j! . S

can be multiplied by 10, j; ! i The results of the impact resistance tests, according to! j j i | j || the Dynstat method, the aged coating side being struck by j j |; the pendulum, are given on an average of 10 test tubes for! 'î i 1 • each exposure time, The size of the test pieces is; j I, j 35; : 50 x 10 mm x by the thickness in mm of the composite material, d d d d 1 d The tensile elongation tests are performed j '. l-jli ·: Ü •:; ; | . according to standard A5TH-D 638.55 on specimens machined in the; :! . >, é; matera to composite.

•! : EXAMPLE 1 d; · A solution of PVF ~ in diinéthylformair.irie on \; s 5; incorporates 3 / u by weight of ïiD-, relative to the weight of PVF9, • the dry extract of the whole being 20 by weight. We coat i j! ! i i i this composition on transfer paper so as to obtain i S m; *. ;! after evaporation of the solvent at 140 ° C, a 25 micron film and one: · 50 micron thick film;

:! J

’I1 Ö! For comparison, we are preparing a PVF film „without! i j! ^ i i ·! j TiO 25 microns thick. j i; ! 2! j | j One of the faces of each of the three films is sprayed:; 'j se a 15% by weight solution of solid polyesterpolyurethene | ; ·. (DESM0C0LL 500 from BAYER) in dimethylacetamide. We evaporate on the 15th! solvent by keeping the films for 5 minutes at 150 ° C. in a ventilated oven. . not a word

; The thus treated faces of the films are applied J

,, i on a sheet of AB5 (UEIKRAL S.E. of CHEMICALS UGIL'E!: ’KUHLMANN) 3 mm thick and glued in press at one temp; . l ·: eruption of 17ÛQC, |

Still for comparison, we stick on a sheet j of ABS, under Iss conditions above "a 5D microns thick film based on polymethyl methacrylate (PMMA) loaded at 3%! ! s weight of T-iO ^ · j '*' The composite materials thus obtained are aged; j under the conditions previously mentioned. j »i The results of the impact resistance tests and of the longest in tension are given in the tables below. By way of comparison, the results obtained on i • the unseen sheet of AI5 are also golden:! 1; / '! . ! ! * t i! i t \.

• t 1 i .... .. j l-5I3 j! :. ______________________, ____—--- η j i! · * *.

! ; ! ; Impact resistance expressed in% cie î, · *! not a word '; the initial value at time 0 i [i I 'Duration ~ -—--—----------'! : ,, ... Material comnnsite,; a * exposicion _ _'______ | 5; · ’(hours) ABS (PVF2 + Ti02) (PVF? + Ti02) PVFp (PMKA + Ti02)! Il 25 μ 50 μ 25 μ 50 μ i | ·: - ί ~~ Ί ΐ {ί; 1; ! : ο 100 100 100 100 100: j:; " not a word; 100 32 98 100 54 TD j • I j I 500 28 09 95 34 35 j 10; i 1 * 000 24 6B 06 30 30 d; i! i i; ; H 2,000 23 40 70 -— 25> i il! ΙΓ '* "'“ “_i i!}; J ii ·! I j i:. I

; | i · Elongations at break, expressed in y? J

not a word ; · Duration —--------------—-— -—: - ~ d! i j! d <Exhibition ____ Composite material ________ | I 15 ;: (hours} ABS (FVF + TiC)) (PVF2 + TiD2) PVFj (PMMA + TiOp; (ii; j | M: 25 μ 50 μ 25 μ 50 μ j 1 1 —.1 n il i. .> * »· M '" ».ii ..» l ir Μ .τ'ΐ.ι ··· »·» ^ - I 11' »» ι · »ιι · ι · - · n" J ·· * -1 * ► "·· '*" * "I"' * "1 r '^ ^ I i1!

j f; J

i | If 0 30 2B 29 28 27!

! j j j I

i; 1 00 15 28 28 22 25.! I! j! ! ! 500 10 25 26 14 20 i J! ; · | 20 *; U 000 7 20 23 9 13 d d * * | j j 2,000 4-18 - 7 ‘10 j \> ^ | t _ î i- il “'' i I! ; i i * i: ··; i ii; · I î j! i. Μ! | i; S EXAMPLE 2 d! ί II In the manufacturing conditions of example 1 we pre-i i M i „! j! ; shields three composite materials based on ABS, 3 mm thick d j. (\ 25. and PVF whose charge of TiO ^ is replaced by: j | l; | a) 11) a- by weight cJ zinc oxide relative to the weight; :: h of pvf; ; ! ; · 4 i y; l ...- -

L.O

,.,. JF · - “· J

* t * i i ’||; b) a mixture of anti-ultraviolet agents comprising; ! ; I by weight relative to the weight of PVF: î i; , ^,

j), 1 of a substituted benzotriazole compound J

’! ; (TIN U V11 "P) i 5d; and 0.6 ‘j of a sterically hindered substituted amine; I | (TINUVIN 770),; j II c) a mixture cn3.culê by weight compared to the weight! ! i; ! I | PVF2 from; i l | » 1.5 Çb of cadmium red (Red 125 FBA) î! i i; î0 d | and 1 5¾ of iron oxide of red shade (Red 720) t j j j! <S * j! The results of the impact resistance tests and {! The tensile elongation after aging are given in | J î \ ί M „·; ; i the table below. i *; 1 * \ "·" <i; j _ .____. _____________ ____; j; j Duration 'j 15 ’of exposure Test a Test b Test c! ,. ; j i; in hours \ | j · -----_ | --- ^ - j j || Coating thickness; I I ment PVF „25 μ 25 μ 50 μ! He! 2 ^ r ^; d d d -....... III · -.-.- .. 1. ..... ,, 1 II —.1 .. ......... —— ...-, ....., 11 ........... - - —— j ÎResistances; »u choc 0 100 100 100 j 20! after aging -: 7 '· * .., r'. , 100 98 97 -89 i. expressed in p oe la | ! ! initial value eu 500 81 93 79 I j; tBmpS ° 1.00064 66 53; i! ; i i; , -—, - --— --— --—-—-—----.

| |: TRACT lON-AST’H 0 25 29 29 d | 25 * Extensions to the rup- 100 24 27 25! i: ture after aging- <j j menr expresses; in / at,! i · '1 .000 17 19 15! 1 i · l t -: (t _ ----. | Il -! ... _ _ I____ j _ ____ i! I ’i

MS I

:; j EXAMPLE 3 j! 30: A .me so3.uticn of PVF- in dimethylformamide is included; . . * ·! I: j corpore 2% a- * weight of carbon black (Black 900) compared! ; ; · By weight of the pF ^ "the dry extract of the whole being 20" by weight. This composition is encircled under the conditions of 3 'ex er—, | i I pie 1 de fsço * f ·· obtain after evaporation a 25 micron film; t · i \ i /; M! lx: ·; '; .......' '' î *: - · î j!.!; thick. î ti *;

I M

! Still under the conditions of Example 1, we treat; • »5! j | j one side of the film with a 15 ‘p weight poly solution; :: esterpolyuréthnne nnlj.de in the djméthylncétann det

: 5 ·: In addition, non-pigmented ABS is extruded (UGIKRAL SE

: ·! »: Unine Kuhlmann Chemicals) on a single screw machine; ; ! diameter 90 mui, length 20 diameters, equipped with a die, II! ! i flat 70D mm wide and adjusted to obtain a thick plate; “; ! j! " · 5 mm, the machine temperatures range from 200 to! i:! 10: j 24D ° C, the die being regulated at 210 ° C. The speed of rotation j j! ! j. | of the screw is set to 30 days / minute and the flow rate is 120 kg /! i! hour. !

î I ". I

I j \! ii The PVF film? obtained previously is held at tem- d d d:,. ,! The ambient pereture and the treated side is applied to 1ΆΒ5 of i

Mi. . . ! 15!. continuously by means of the polishing train of the ex line! j. - i! . trusion, the cylinders of which are regulated at dES temperatures: t t | | giant from 90 to 110 ° C.

II.

i The results of the impact resistance and al- j i j I j j long-term tensile tests after aging are given in! * 20jI table below, i i * î · ...____ ______________________ i | Shock resistance i Duration of exposure after aging Elongation at! . expressed as% of the rupture expressed j initial value βπ% 25! at time 0 J. I -; ----------- j 0 100 35 ”'! ; 100 97 32 i i j: 500 92 31 i 1! 1,000 72 26; \ i · * j l | __ _____! ! i

/ I j J

i j; 1 Μ j i: i

Claims (6)

# L.B ___ D Ni! : S REVE M TU C A T10 tv 5 d! ; I ί 1. ; ! * *! i î j 1 - Composite material with improved mechanical properties; i jj improved after aging whose main element is a ter-! ! !] acrylonitrile-butadiene-styrene polymer characterized by the fact that on the day! j î i 5: i minus on one of the more slender surfaces of the polymer element i: i! i, is fixed a coating of polyvinylidene fluoride containing a, j * i! * \ | mineral or organic filler protective against ultra-rays! | j j purple. i! ·! he ! 2 - Material according to claim 1 characterized in that the i. . ; 10; the polyvinylidene fluoride coating is of maximum thickness J J ten times less than the thickness of the terpolymer element without | ! * î i | | or the coating thickness is not more than 400 microns. I! J! ! i j. , I i! I 3 - Material according to claim 2 characterized in that the! | | j! j j coating thickness is less than 100 microns. ; ! ! ! j! Ü. I 5 ; : 4 - Material according to one of claims 1 to 3 characterized in i | j i i | what the coating contains from 0.1 to 50% by weight of filler! | 1 t! ! mineral, i i; ! I • * î; j! 5 - Material according to claim 4 characterized in that the I i [i ·: mineral filler is chosen from oxides, salts or ·]; "20 '" metallic powders. i: i *! ? ; if ; :; i >; 6 - Material according to one of claims 1 to 3 characterized in j! ; · I; what the coating contains from 0.1 to 10 ί by weight of filler j; organic, ! i i: I; t • I ï - Material according to claim 6 characterized in that the I 25 organic filler is chosen from pigments or agents \ nb s otbante d'v11 ra-violet. !