JPH07507590A - Paintable polyethylene - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Paintable polyethylene The present invention relates to functionalized polyethylenes. In one aspect, the present invention has at least one double bond and at least one functional acid group, such as maleic anhydride. Concerning polyethylenes grafted with unsaturated organic compounds containing phosphoric acids, etc. While in another aspect, the present invention provides that these functionalized polyethylenes It is associated with high compatibility with thermoplastic polymers containing functional groups. one state In this case, the present invention can be used without surface pre-treatment or special primers. Molded from paintable blends of functionalized polyethylenes and the above polymers. While in another aspect, the present invention relates to products that are substantially similar to each other. The combination of functionalized polyethylenes and certain polyurethane foams that exhibit perfect adhesion It is related to laminates.

Thermoplastic polyolefins (TPOs) are lightweight, durable, and low cost. as well as exhibiting other desirable properties, they are used as constituent materials for a variety of consumer products. It has steadily grown as a result of being used as a. For example, in the automobile industry While these materials are used in various interior and exterior parts, they are also used in the manufacture of household appliances. Manufacturers are using TPOs in everything from support structures to decorative fanoires. I am using it.

Although TPOs have many desirable properties, they also have certain undesirable properties. attributes, particularly those that do not accept paint or decorative prints. have. TPOs are, by definition, hydrocarbon polymers, typically is polyethylene, polypropylene or ethylene-propylene rubber, etc. These do not exhibit polarity as they are. Many paints are polar and therefore have no In order for these to be able to adhere to the surface with the desired degree of fastness, We need to give the surface some polarity. There are many different proposals for this problem. This has been done with varying degrees of success.

One relatively common solution is to apply a primer to this TPO. It's a method. Primers are typically halogenated polyolefins and aromatic The composition includes a solvent such as polypropylene chloride and toluene. ply Although marketers are generally recognized as effective, they are expensive and , these applications are an extra step in finishing this TPO product.

Another way to enhance the paintability of TPO surfaces is to apply physical or chemical treatments to the surface. This method involves etching the surface or irradiating the surface with plasma. child Although these methods are generally effective, they are of course more complex than primer application. and therefore more difficult to control in terms of quality and consistency from part to part.

Additionally, these techniques are generally more expensive than the simple application of a primer.

Yet another technology, which continues to grow in use, combines TPO with other thermoplastic polymers. blend or incorporate one or more polar groups into TPO, or Modify the physical and/or chemical properties of TPO by doing both. It is a technology that For example, Mitsun.

Another U.S. Pat. No. 4,946,896 includes 20-80% by weight polypropylene , ester unit of ethylene and alkyl acrylic acid or methacrylate and unsaturation 5-38% by weight of an ethylene copolymer consisting of dicarboxylic anhydride and Paintable TPO containing 5-70% by weight of tyrene-propylene rubber is taught It is. U.S. Pat. No. 4,888,391 to Domine et al. ethylene/acrylate/acrylic acid terpolymer and polyolefin as continuous phase. A paintable polyolefin composition comprising a blend of fins is taught. It is.

Yet another teaching is provided by Aleckner, Jr. et al., US Pat. No. 4. 945. 005 This is a copolymer of ethylenically unsaturated carboxylic acid and ethylene. -25% by weight, 3-50% by weight of ethylene-alpha olefin copolymer, optional crystalline propylene homopolymer or copolymer, 5-50 ply of inorganic filler % and polyethylene or copolymer of ethylene and alpha olefin Paintable TPOs containing 10-35% by weight are taught. above and Although other modified TPO compositions have shown some efficacy, none of these Considering the ease of assembly and cost, etc., the results are not completely satisfactory.

The paintable thermoplastic composition according to the invention is based on the weight of Δ polyethylene. at least about 0.01% by weight of at least one double bond and at least one An unsaturated organic compound containing several functional acid groups, which can be used to make grafted polyethylene. at least about 50% by weight, and B. Contains at least one thermoplastic polymer containing a polar group.

Preferably, the polyethylene is high-density polyethylene; Both make up about 80% by weight. The thermoplastic polymer is preferably nylon or or polyurethane. In one embodiment of the invention, these compositions are molded into While producing various products such as automobile parts, in another embodiment, This grafted polyethylene (g-PE) is laminated onto polyurethane foam. . In yet another embodiment, the g-PE and other materials such as wood, metal and latte When blended with other materials such as paints, this provides excellent adhesion to these materials. show. The paintable thermoplastic composition of the present invention is a blend of g-PE/other materials. without the use of a primer or preliminary surface treatment, as is possible with many You can receive the paint and keep it.

In the present invention, a compound containing at least one double bond and at least one functional acid group is used. Any ethylene polymer or copolymer that can be grafted with an unsaturated organic compound Combination is also possible. Ethylene polymers and copolymers fall into two broad categories: i.e. produced at high temperature and pressure using free radical initiators, and coordination It is produced using a catalyst at high temperature and relatively low pressure. The former is generally known as low-density polyethylene (LDPE), and these It has a branched chain of polymerized monomer units hanging from the remer backbone. characterized by The density of LDPE polymers is generally 0910 0.935g/cc.

esters produced using coordination catalysts, such as Ziegler or Phillips catalysts. Thyrene polymers and copolymers generally have Linear polymers are essentially free of branched polymerized monomer units. - known as a class. Density is generally between 0.941 and 0.965 g/cc High-density polyethylene (+-(DPE)) is typically a homopolymer of ethylene. and the number of branched side chains contained in this is the same as that of ethylene and a-olefin. compared to various linear copolymers. HDPE is known (also known as species) are commercially available in various grades and are useful in the present invention.

alpha-ol having 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms; Linear copolymers of at least one lefin and ethylene are also available (known , commercially available and useful in the present invention. In this technical field As shown, the density of linear ethylene/alpha olefin copolymer is is a function of the length of this alpha olefin and the ethylene content within this copolymer. The length of this alpha olefin is a function of the amount of the above monomer relative to the amount of As the length increases and the amount of alpha olefin present increases, this The density of the copolymer becomes lower. Linear low density polyethylene (LLDPE) is Typical carbon atoms having from 3 to 12 carbon atoms, preferably from 4 to 8 carbon atoms. Co-operation of fluorophore olefins (e.g. 1-butene, 1-octene, etc.) with ethylene polymer, which is sufficient to reduce the density of this copolymer to that of LDPE. It has a significant alpha olefin content. This copolymer contains more If it contains fur olefins, its density is less than about 0.91 g/cc. Such copolymers are ultra-low density polyethylene (ULDPE) or is known as very low density polyethylene (VLDPE). these lines The density range of polymers generally ranges from 0.87 to 0.91 g/cc.

Both materials produced using free radical catalysts and coordination catalysts The method of manufacturing is well known in the art. These materials and manufacturing methods A discussion of both laws can be found in U.S. Patent No. 4. No. 950゜541 and the words therein. and the patents referenced herein, all of which are incorporated herein by reference. be incorporated into the book. HDPE is the preferred polyethylene for use in the grafting process of the present invention. It's Ren. Preferably, the HDP E suitable for grafting is about 10-25 g/ It shows a melt index of about 0.95-0.965 g/cm3 at 10 minutes. Indicates density.

In the practice of this invention, the polyethylene polymer or copolymer described above is grafted with containing at least one double bond and at least one functional acid group, Any unsaturated organic compound can be used. Preferably, this polymer chain is The compound to be converted contains a double bond that is conjugated with the double bond of the acyl group. and preferably the compound is moderately polymerizable and readily undergoes chain transfer reactions. tend to produce relatively high molecular weight polymers. Typical examples of the above compounds These include maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, chloro Acids and anhydrides such as tonic acid, alpha methyl crotonic acid, cinnamic acid (which may be present) ). Maleic anhydride has at least one double bond and at least Preferred unsaturated organic compounds containing one functional acid group.

The content of unsaturated organic compounds in this grafted polymer is low (approximately 0.01 wt. %, preferably at least about 0.05% by weight. This unsaturated organic compound content Although the maximum amount of may be conveniently varied, typically this maximum amount is about 5% by weight or less. and preferably less than or equal to about 2% by weight, and more preferably less than or equal to about 1% by weight. be.

Any of the known art, such as U.S. Pat. No. 3,236,917 (which is cited (herein incorporated by reference), etc. The unsaturated organic compound can then be grafted onto the polymer. example For example, the polymer is introduced into a two-roll mixer and a relatively homogeneous mix is obtained. Mixing is carried out at a temperature of 60° C. until a compound is obtained. With this unsaturated compound Add a free radical initiator such as Nzoyl peroxide, and this graph These ingredients are mixed at 30° C. until the conversion is complete.

A preferred method of grafting is U.S. Pat. No. 4,950.541. (the disclosure of which is incorporated herein by reference), as a mixing device. A devolatilizing twin screw extruder is used. Preferred alternative grafting methods are taught. This polymer and unsaturated in an extruder at a temperature at which the organic compound melts in the presence of a free radical initiator. These reactants are mixed and reacted. Preferably, the extruder is maintained under pressure. Inject the unsaturated organic compound into the retained zone.

In one embodiment of the invention, polar groups such as carboxyl or hydroxyl After blending g-PE with some thermoplastic polymer containing groups, molding to produce a molded product. These polymers include ethylene and acrylic acid. Copolymer of ethylene and carbon monoxide (ECO), copolymer of ethylene and carbon monoxide (ECO), poly Amides, epoxies, polyurethanes, polyesters and various polar group-containing Contains polyolefins. These thermoplastic polymers are filled with the g-PE. As a result, blends of these two species can be mixed. They do not cause separation during or after. Minutes these materials show Although the molecular weight can vary widely, the thermoplastic polymer used in this embodiment with respect to compression molding The mers typically have a melt value of 0.01 to 3.000, preferably 01 to 300. According to index (AST~I D-1238, conditions 190°C/2.16kg) +2) measured by The melt index for injection molding is typically 0.05 to 1200, preferably 0.05 to 1200, preferably 0.05 to 1200, preferably 0. It is from 5 to 100.

The g-PE is at least about 50% by weight of the g-PE/thermoplastic blend. , preferably a small amount (about 70% by weight, more preferably at least about 80% by weight) has been completed. Preferably, only one thermoplastic polymer is blended with the g-PE. However, blends of g-PE and two or more compatible thermoplastic polymers are also desirable. It can be prepared if it is available. Heat suitable for polyurethanes and polyesters They are plastic polymers.

This g-g- Mix PE and thermoplastic polymer with each other. Form this blend by extrusion This g-PE and thermoplastic polymer are typically combined to produce a finished product. are individually introduced into the extruder, and prior to extrusion, the Do the mixing. When molding this blend using compression or injection techniques, some These two components are first combined using conventional means such as a roller mill, stirrer, etc. After mixing well, introduce into the mold as a homogeneous mass. The surface of this mold The die head can be made of any material, but is typically stainless steel. Preferably, these surfaces are made of polyester or Film, for example Mylar (Commercial 1) (E, L du Pont de N (manufactured by Emoursand Company) or covered with It is. Products molded under relatively low shear conditions, such as compression molding products molded under relatively high new conditions, such as injection molding. Shows good paint adhesion.

In another aspect of the invention, the g-PE is laminated to a polyurethane (PU) foam. let PU foam has many different uses, and one of particular interest is One is as an insulating material. For example, rigid PU is currently Refrigerator cabinets typically laminated to tajene-styrene terpolymer (ABS) Used as an insulating material within the vignette. However, hard [jPU format] The classic blowing agents for foams are chlorofluorocarbons, and these However, it is believed that it threatens the ozone layer. New blowing agents are under development and these include hydrochlorofluorocarbons, which are A Attacks and melts the BS liner, which in turn destroys the liner and PU pho This results in a reduction in contact surface adhesion between the contact surface and the surface.

The g-PEs of the present invention are produced using a hydrochlorofluorocarbon blowing agent. Excellent adhesion to PU foam. Therefore, using such a new blowing agent, The production of laminates containing ABS and 1’U foam manufactured using g-P This g-PE and ABS are blended prior to laminating the g-PE onto the PU foam. or use g-PE as an adhesive layer between the two layers, or replace the ABS completely with g-PE. −)) By replacing it with E, the contact surface adhesion between the two layers is deteriorated. It is easily done without any trouble.

This g-PE also produces melt blends with wood fibers, such as wood fibers. It can also be used as a binding agent. Such blends contain polymers. Unlike soaked wood, it exhibits excellent dimensional stability and water resistance. These appearances has the appearance of wood, but its surface does not get wet with water, i.e. beads of water do not appear on its surface. arise. These blends also receive and retain paint well.

In another aspect of the invention, the grafted polyolefin or g-PE is Prior to use as a blending component or adhesive, it is Iet-down J or diluted Ru. For example, this g-P as described in U.S. Pat. No. 4,950,541. After producing E, it is mixed with virgin polyethylene and backbrane in an extruder. A predetermined dilution rate is obtained by Left down or dilution rate is g-P Weight ratios of 110 to 10:1 are typical, although this will vary with the end use of the E.

The following examples illustrate certain special embodiments of the invention. all departments and Percentages are by weight unless otherwise specified.

Example 1-42 and Control C-1 to C-42 Automotive paint adhesion test samples preparation In all samples except one (Example 39), this grafting Polyethylene was prepared according to the procedure described in U.S. Pat. No. 4,950,541. High density polyethylene (HDPE, g, MAH) grafted with maleic anhydride ). Then this grafted polyethylene and thermoplastic polymer Werner and Pf 1eidere operated at approximately 210°C. r was fed into a ZSK-30 twin screw extruder. These blends can be removed with one pass. Manufactured products.

Barrel temperature is 200-250°C, barrel pressure is 40 bar, cooling The cooling mold temperature is 85 degrees F (29,4 °C) and during residence in the cooling mold A 50-ton Negri-Boss is operated with a time interval of approximately 12 seconds. Prepare injection molding samples using iInjection Molder. It was. The press plate temperature was approximately 190°C, and the press pressure was 27.7 psi (19 0,85kF) (5 minutes) followed by 83. lps i (572,56kP) ( 1 minute) and operated at a cooling rate of approximately 15°C per minute. Compression molding using a DrakePress (model number 45-062) Sample preparation was performed. Unless otherwise indicated, this compression mold and da The surface of the chair head was made of stainless steel. Molding these samples A 6" x 6" x 3/4" plaque was created.

Paint adhesion test protocol After cleaning these samples, they were treated with one of two automotive paint formulations. These were painted. Paints that cure at 180 degrees F (82,2 degrees C) are , two-component polyurethane coatings combined with white paints and isocyanates. industry (e.g. PPG Industries).

317LE19747-3RA white paint commercially available from Inc. and Durc thane (trademark) LE 800 series), while 250 degrees F (121 , 1°C) are one-component systems (i.e., thermosetting melamine formaldehyde). It was a polyurethane or polyester paint system (cross-linked with aldehyde). Each plastic After applying a single top coat (no primer), bake for 40 minutes. went.

ASTM D3359-87 cross knot and tape peel test and GM Initial paint adhesion was measured using the dime scrape test of -9506-P. this If these tests have been successfully passed, these samples are then tested with GM-4466-P. The specimens were immersed in a 100° F. (37.8° C.) water bath according to the following procedures. Then bubbles and wrinkles Each sample was tested for If you pass this exam, these samples A second set of cross/% sochi and tape peel tests and dime scraping tests were carried out. I accepted it.

The above test results for samples prepared by injection molding are reported in Table IA. Compression composition The above test results for the samples prepared in the form are reported in Table IB. Table IA and The explanation of IB is reported in Table IC.

Table IA Key points for automotive paint adhesion tests on samples manufactured by injection molding G, oIrrPu−SoΔ=7. sn, s 2sor (+x+, +c) xso (+n, +c+ 42 HDG, OI/TrlJ-908 = 7.572.5 2 50 "(12+, lcl 250 (12Llcl 43 HDG, 02/TI' U-SOA-7,5/2.5 250F (12+, I C1250 (121, I C141 (DG02/Tt'U, 908 = 7.51'2.5 250T'+1 2nd c1 250+121. lc) -15HDG, 01 250F (121, 1C1250(121,IcI-6HDr'E25]557r'l:It)= 7/3 (J-2, 51250F + 12th C1250 (120C)] C・l II DG, Ol/Nylon=9/l 250r'+121. I CI 250 +121, I C12C-21 (DG, 02 (SO "(52, 2022a) (+21.+cl IC・3℃, 01/Nylon-8/2 250F ( +], I C1250 (1’20C) IC7! ) [)G, 02/Nylon -312250F (121, I C1250 (121, I C1lC゛510 ] (ko02) Nylon-4, +2! l0F(+21.IC250(Ivy21.I C1IC-6) (DG041Atur+=042:to 3JC=V4/1(v e2J, 6: moldloo, melow 13011sOF (Sl, 2C1IS0 (Sl, 2C1OC・FHDG, OJ/AIuncGJ2] 0/T!Ic:5 7J/1 (vg, 4.mold lω, mel+ 4501 13OF (Sl , 2C) lSo (Sl, 2C10C1sH[:nicoQJlΔLLin e■4?30/131e=5/-+/l(va, 4.nIold I 50.n tel+4501 1 SOF+82. I CI’ So (Sl, 2 C) OC-’) 1IDC, OJ/A+unc ■4230.6/4 (v, J, n+oldI(\), n+el+45011sOF(Sl, 2CIIsO(Sl , 2C1OC1o 1rDG, Q41A++Cobae()4230gG+4(va ,4. nIold　150. mc mouth 4501 1so+'(s=, :+ C1l so (52, 2cl OC・l 1 1 (DG, Qj/A+u++c■423 0e61J(vao, L+, 6.n+oldloo, +++cl+43011s O"(S22CIISO(S22C1OC-+2　11Dr'(45355(= =2.31 1sQi’ (Sl,! CI IsOCSr2CI O Table IA ( continuation) Summary C-111 of Automotive Paint Adhesion Tests on Samples Manufactured by Injection Molding Dl’C251558+1410-911(v=’Z, Sl　1601”(Sl ,’lC) l5O(Sl, 2C) 0C-1ft 1101”C25:15 5/l'+41 axis 713 (replacement = 2.51 1801" + note, 2 (11S0 ( Sl, l　C1OC-15HCX’l:25355/l’59so-9/l(” -2-41l Sol” (K2.2 CI I SO (Sl, 2 C10C6 16110G, G! 1Aua+cQaul=614(vt, 4.nIold　l oo, rucl + 4501 l S (1 "(Sl, 2 C1220 (10-1 ,4CI　+IC,I7　IIDGαU8l1in■’23n=(di(va ,4. mold l 50. mc++ 450) l SOF (Sl, 2C 1220 (IQ4.4 CI +IC-1511DGαU8+cv+cGJ23 0=674(v禮、) 1.6:nIold 100nIcl+4301 1 SOF (Sl, 2 C1220 (l()4.4 C10C-19HDT’C 25] 55 (v-2-411sOF (Sl, 2 C1220 (lo4.4 C 1OC, 20) (DPεu355/r’+410=+7/3(vllMIIsO F(Sl, 2C1220(IQ-1, 4CIOC, 2t HOPc2S3SSr PIa + Ch1f3 (v-5"r l5OF (Sl, 2C) 220 (provided, j C) txinlC, 221 (Drε25355c'+a+O=9/1(v=2 ．． 511sOF(Sl, 2C1220(104, dClOC, 21HDl'll :25:155/r'59sO=97I(1oMl 1sOr'(Sl, 2C1 220 (10-1, 4c+ +IC, 2J, +4DC, o direct (STEEL125 0Ff+121. IC+250 (+21.IC1t17) 4IX 0f (N4y 1250F (+21.1c1250f+21.1C100++1C,?5 1 1Dr’[l0062 250 “(+21.lC1250(1:!1.ICI 0C1261(Dl'E2S'1551'111410=9/l(■], 41 250 "+121.IC+ '50 (121, lcl nD27 1+DFC2 5] 551'l'591i axis 911 (2.4+'!50121.IC+2 50+121. IC+ 13 Table IB Summary Table IB of Automotive Paint Adhesion Tests on Samples Manufactured by Compression Molding (Continued) ) '! 2 1(DG, OZ 'l5OF(1'l!1.lcl'!50t121 ．． 1c) 33 1 (DI’C10052/HDG, 01=2.5/7.5 25 0F(+21.Ic1 250(121,Icl'n HDI'l:lo)6 2/1lDG, ol-1,376,6250FII20C1250 (12th C) 35　1(Dl”EIGχ′)Jl(%01=515　25OFF121.lc l　250+121. Icl '36 HDr'CICA+2/HDG, 0l- 6,6/3.3 250 "[121JC1250(+21.IC+'31H Dr +0062/HDG, 0l-7,572,5250F (+21.IC I 250 +121. I C+3S l(D!'Cl0G5Z/shiLDrεH , M to lI[LLGh515 250FT+21. IC+ 250 (121, I C+ A39 LLG/CI'A・EΔ8 to 9/l 25OF<121. IC 1250 (120C1440) IDC, 01fT'; 410-3/'2 tsO F(!d, 1cl 220fI country) C1-’l HIX:+, Ql/D(IW1 cz■2047! l614 1sOF (Sl, 2C1220 (lOJ, 4cl) 3'12 8DG, OI/930 (Rberglus) = 9/l 250F (1 21, IC+ 250 (+21.lC13C-2SHDr'E1006M'+4 10drzIliOF(g2.2c1220(+04.4C12C49t[[) r’C/CPAJExxxt1or=7fZ/1250F(121,1c1250 (+2+, electric C) C-30HDG, O1/938 (Fiberzlassl=9 /l　2SOF　(121,I　C1lsO(1’!1.I　C1IC・31　 HDr'C/'l'+410=s/2 250F (l':!1.lc1 250 (121, lcl IC・32 + (Dr’CIQD6Vpolycstcr= 9.57.5 250FC+21. lC1250 (121, lcl IC'53 1 (Dr' mouth 1α) 5Vpolyts+cr=9/l 250F+121. I CI 2501121. I C1 electric C, 34HDGOI (1'clon1 250F (+21.I CI 250 +121.I C1OC, 351(D rmouth 1αδ2 250F(+21.lcl 2so([z+, IcI.

C-361(f) r'mouth 10%: υ919σ'ilx: rgmusss'5911 25Or’ (l?Ij C1250 (1, I C1OC・37) [)ρro 1006193αTi1xrHlass) = 9/l 250r’ (121, I CI 250 (+’! 1.1 c 戟@0 C3S 1(Dr’EIC”j2/’DIl(1’+kr, 1assld/l 250 "(121,lcl　250(121,lcl　OC3wa)[)r'CI C:ZG'J):l\ITity,:+Furnace 5s)dHa250F+121.1c 1250 (12!, IC1OC-:0 11Dr’clc+yIZ/I)CR6 67='), 5/, 5 250F (121, lcl 250 (121, Icl Oc=+1(DIY:lQ'a2/DIEIZ%7=')/l250"11 21. lcl 250 (121, lcl 0C-1,? IID!'il;25 035? 50r(!21.ICI’!50(+211cl O table IC Commentary on the composition of Tables IA and IB HDPE: High density polyethylene MAH: Maleic anhydride MI: Melt index PE: Polyethylene (v-2, 5) The injection molding speed readings for two different molding conditions are respectively For example 2 and 5 (v=0.2-1.6) Injection molding speed readings for many different conditions 02 to 1,6 (moldloo) The molding temperature in injection molding is 100 degrees F (37 degrees 8 degrees C) is (melt430) The melting temperature in injection molding is 430 degrees F (221 degrees 1 degree Celsius) ) is (My Ia r) Attach MY Ia r film on the surface of the steel mold 919: Certain Teed fiberglass 5th 919930: C ertain Teed fiberglass 93093B: Certain Teed fiberglass 93B93X: Certain Teed fiberglass Iverglass 93XATTANE (R) 4230: The Dow Chem Ultra-low density polyethylene CPA crystalline polymer manufactured by ical Company Riamide DER667: Dow epoxy resin 667EAA made of ethylene and acrylic acid Copolymer EAAG: Contains 10% acid, grafted with 1% MAH. Ethylene/acrylic acid copolymer ECO with a root index of 2: ethylene and carbon monoxide copolymer (-carbon oxide is 10% by weight) Exxelor: Exx Exxelor VA1830, which is commercially available from on, is grafted with MAH. Tyrene/propylene copolymer HDG: HDPEHDo grafted with MAH , 01: HDPE10062 grafted with about 1.5% by weight MAH: This The MI of the grafted product was approximately 1 g/10 min. HDo, 02: HDPE25355 grafted with about 1.5 wt% MAH : The Ml of this grafted product was approximately 2.5 g/10 min. HDG, 04: about 25 g/Ml grafted with about 1.5 wt% MAH 10 minutes and the density is about 0. 955 g/c-m3 ethylene/1-pro Pen copolymer: the MI of this grafted product was approximately 2,5 g/10 min HDPE 25355: MI is approximately 25g/10 minutes and density is approximately 0°955g /cm” ethylene/1-octene copolymer HDPE 10062: MI is about 10 g/10 min and the density is about 0°962 g/cm3. -Dowlex (R) 2047: Ml is approximately 2.3/10 minutes and density is approximately 0 ．． 917g/cm3, The Dow Chemical Company Ethylene/1-octene copolymer LLG manufactured by AlliAlle Grafted using about 1% by weight of MAHCapron 8207 manufactured by d-3i. Dowlex (trademark) 204Nylon: Ca manufactured by AlliAllled-3i pron 8207P1410: Primacor(TM) 1410 is T Manufactured by h e D OW Chemical Company, Ml is approx. 0.5 g/10 min and an acrylic acid content of about 10% by weight. /acrylic acid copolymer P5980: Primacor(TM) 5980 is a Manufactured by Chemical Company, Ml is approximately 300g/10 minutes Ethylene/acrylic acid copolymer with an acrylic acid content of about 20% by weight body Po1yester: Dow's research material polyester TB90050RUI Poly□]: Jef famine (trademark) manufactured by Texasca M-2005 Talc: Microtuff (trademark) 1TPU manufactured by Pfizer : A trademark manufactured by The Dow Chemical Company. Thermoplastic polyurethane TPO-80A: PELL ETHANE (trademark) 2102-80ATPO-90A: PELLETHAN E(trademark) 2102-90AC Comparative Example is shown and is not an example of the present invention. stomach.

Results and conclusions Column 1 of Tables IA and IB reports the composition of each of these blends.

A description of these compositions is reported in Table IC. In column 2, depending on the curing temperature Report the properties exhibited by the paint, report the actual curing oven temperature in column 3, and The test results are reported in column 4.

In column 4, "4" indicates that the painted plaque is cross-hatched laterally after the initial test and the water immersion test. It means that he passed the Tutsi test and the dime scraping test.

"3" means that the painted plaque was tested by crosshatch test and dime scraping in the initial test. The water immersion test passed both the crosshatch test and the dime scratch test. This means that you failed one of the exams.

``2'' indicates that the painted plaque was tested by crosshatch test and dime scraping in the initial test. The water immersion test passed both the crosshatch test and the dime scraping test. This means that he failed both exams.

``1'' indicates that the painted plaque has been removed by initial crosshatch testing or dime scraping. This means that you failed one of the exams.

"0" means the painted plaque failed both initial tests. are doing.

Molding conditions have a direct effect on the surface properties and therefore the coating that these plaques exhibit. Gender is affected by it. For compression molding equipment, these samples are (free 5 surfaces) to bulk. injection molding In the case of shaped devices, after melting these pellets, these moldings are Cool from to bulk. The pressure exerted on these two types of moldings also depends on their They are different as well as the refractive index.

The injection molding shear index for PE where Ml is Log/10 min is approximately 2000-5 000/second. The effects of these two different thermal and mechanical histories are shown in Table I It will be seen from the results reported in A and IB. For example, manufactured by injection molding While the paint adhesion exhibited by C-1 is only at a marginal value, Example 2 manufactured by compression molding 6 is reported to exhibit essentially perfect adhesion.

From the comparison between C-24 and Example 7 and the comparison between Example 11-12 and C-34, this The effect of the molded surface on the paintability of the plaque can be seen.

In the first comparison (between injection molded samples), the plaques of Example 7 were C- Better than 24 plaques, but both of these have acceptable levels of paint It showed no adhesion. This crosshatch and tape peel test using a range of scores, where any score below 3B means failing this exam. be. The score of the plaque of Example 7 was 2B, but the score of the C-24 plaque was 2B. The score indicated was O.

These results indicate that the Mylar surface is not suitable for the paint adhesion properties exhibited by this plaque. This indicates that some kind of improvement has been made.

In Examples 11-12 and C-34, the same procedure was performed for compression molded plaques. Although effects have been reported, the results here are much more pronounced. Example 11- 12 exhibits essentially perfect adhesion, while C-34 (Teflon™) (manufactured using treated mold surfaces) have been reported to exhibit virtually no adhesion. There is.

For plaques made by injection molding, Examples 1-6 showed acceptable paint adhesion results. It has been reported that Control 1-27 shows unacceptable paint adhesion results Most, if not all, of this is due to the processing method (injection molding). It can be attributed to (form). An assembly similar to the one shown above, manufactured using compression molding techniques. The composition exhibits acceptable paint adhesion properties.

Example 8-42 Compression Molded Plaques Made from a Wide Variety of Compositions It has been shown that these exhibit excellent paint adhesion properties when applied.

These compositions include LLDPE (Examples 8-9) or HDPE (Examples 8-9). 10), g-PE itself (performed) Examples 1l-12l and various thermoplastic polymers or easily blended with fillers g-PE, such as polyamide (Example 16-17), epoxy (Example 18) -19), nylon (Example 26), fiberglass (Example 13-14), Includes g-PE blended with talc (Examples 29-30) and the like.

Controls 28-29, 31-33 and 35-42 were prepared either alone or with various thermoplastic resins. Efficacy when using ungrafted polyethylene blended with reamer or filler It shows results.

Examples 42a and 42b. In both examples of additional automotive paint adhesion tests Then, a 1:1 blend of HDE, 04 and P1410 (see explanation in Table IC) was prepared. Prepare and injection mold 65” x 2°5” x O,075” plaques of this blend. These plaques were prepared using the two-component polyurethane described in Examples 1-42. After painting with a white top coat (no promoter, no primer) of Example 1 The test was carried out using all the procedures described in -42. Complete paint contact for both examples. Adhesion was achieved.

Examples 713-44 and Controls C-43 to C-45: Rigid polyurethane foam Adhesion of polyethylene to adhesive sample preparation This rigid polyurethane foam consists of two different hydrochlorofluorocarbons. The Dow Chemical C uses a foaming agent.

mpany application polyether polyol/PMDI This was the base formulation. We demonstrated that these foam samples exhibit freeze stability. To ensure that the final in-situ foam density is 21 lb/ft (33,64 k g/m3) to 22 lbs/cubic foot (35,24 kg/m3) I made it so that Standard for measuring flow properties of rigid polyurethane foams These samples were prepared using an industrial equipment Bre11 mold.

Add these polyethylene panels to the bottom, middle and top of the mold. was placed and allowed to foam so that the effect of varying foam density and texture could be evaluated. This connection The results of the wear test are reported in Table 2.

Table 2 C-454IC):, 01/Doulax() 2047=1/9 Fail Fail result A description of the various compositions is provided in Table IC. rPassJ must be completely adhesive , i.e., the relationship between this polyurethane foam and g-PE under stress. This shows that this form fails before the contact surface between them fails. rF ailJ indicates incomplete adhesion, i.e. under stress this The contact surface between this foam and g-PE must fail before the foam fails. It is shown that. As the results in Table 2 show, g-PE Excellent adhesion properties for polyurethane foams produced using Rocarbon blowing agents. while ungrafted polyethylene did not. C-45 is g-P It has been shown that it is preferable to have E present in certain minimum amounts.

Examples 45-46 and Control C-46 and C-47 Polyethylene/Wood Fiber Blends thing sample preparation 5 using a Haake 90 system operated at 190°C and 60 rpm. A melt blend of polyethylene and rinsed fibers was produced in minutes.

After heating this Haake to operating temperature, polyethylene is added and blended. while melting. Next, the pickled fibers were added and melt blended for 5 minutes. next By extruding this melt blend, we can obtain the appropriate sample size for testing. The results are reported in Table 3. LDPE723 has Ml of approximately 8 g/10 minutes The Dow Chem has a density of about 0.916 g/cm3. It is a branched PE homopolymer manufactured by ical Company.

Tendan vinegar! ``Rainbow fall Haruno hヱ'' Bojie crawl μ crossing l ll heart A, too raw fiber and virgin poly Part B using ethylene, using highly refined fiber and virgin polyethylene *5 0%JiMlft+50%LDPE 723** 50%JIIft+-40% LDPE 723+10%HDG, 04 spirit! As reported in Table 3, the presence of g-PE in this blend increases elongation and The tensile strength of this composite was significantly increased without adversely affecting the density properties. Ru. This effect was observed in compositions containing raw wood fibers and compositions containing refined wood fibers. seen in both.

Although the invention has been described in detail using the above embodiments, such details are not included for purposes of illustration. for purposes only and should not be construed as a limitation on the invention. Claims below Unless departing from the spirit and scope of the above range, the ethylene copolymer used in the present invention The combination is a copy of the pendant oxygen-containing group and the translation of the multiple amendment document) submission form (patent Article 184 of the Act - December 5, 1994

Claims (24)

[Claims] 1. A. in an amount of at least about 0.01% by weight based on the weight of the polyethylene; unsaturated organic containing at least one double bond and at least one functional acid group The compound contains at least about 50% by weight of the grafted polyethylene polymer; do B. Paintable thermoplastic containing at least one polar group-containing thermoplastic polymer Plastic composition. 2. The composition of claim 1, wherein said unsaturated organic compound is maleic anhydride. 3. The composition of claim 2, wherein said polyethylene polymer is high density polyethylene. . 4. the polyethylene polymer comprises at least about 70% by weight of the composition The composition of claim 3. 5. The polyethylene polymer is treated with maleic anhydride in an amount of at least about 0.1% by weight. The composition of claim 4 grafted with. 6. The thermoplastic polymer is polyurethane, polyester, epoxy, polyamide. and at least one polar group-containing polyolefin. . 7. A. (1) at least one double bond and a small amount in an amount of at least about 10% by weight; at least about 0.01 unsaturated organic compounds containing at least one functional acid group; (2) ungrafted polyethylene polymer in an amount of % by weight; Polyethylene blends consisting essentially of modified polyethylene polymers and about 50% by weight, and B. At least one thermoplastic polymer containing a polar group, A paintable thermoplastic composition comprising. 8. 8. The composition of claim 7, wherein said unsaturated organic compound is maleic anhydride. 9. The polyethylene polymer grafted with the unsaturated organic compound is a high density polyethylene polymer. 9. The composition of claim 8, which is ethylene. 10. The claimed ungrafted polyethylene polymer is high density polyethylene. Composition of Range 9. 11. A. By heating and shearing the ethylene polymer in an extruder B. melting the polymer; An extruder filled with this ethylene polymer Inject maleic anhydride and free radical initiator into the chamber of C. This nothingness the polymer for a sufficient period of time to cause the hydromaleic acid to graft to the ethylene polymer. - and maleic anhydride are mixed in the extruder, D. Extrude and collect the product of step (C); E. The product collected in step (C) and This is done by shearing the mixture with additive ethylene polymer in an extruder. Blend them, and F. said poultice by a method comprising extruding and collecting the blend of step (E). 11. The composition of claim 10 for producing a polyethylene blend. 12. An article formed from the paintable thermoplastic composition of claim 1. 13. An article formed from the paintable thermoplastic composition of claim 7. 14. An automobile part made from the paintable thermoplastic composition of claim 1. 15. An automobile part made from the paintable thermoplastic composition of claim 7. 16. A. (1) at least one double bond in an amount of at least about 10% by weight; at least about 0.0 of an unsaturated organic compound containing at least one functional acid group; (2) ungrafted polyethylene polymer in an amount of 1% by weight; polyethylene blend consisting essentially of at least about 50% by weight, and B. At least one thermoplastic polymer containing a polar group , for producing paintable thermoplastic compression molded articles from thermoplastic compositions containing In law, a. contacting the thermoplastic composition with a polyester mold surface; b. This thermoplastic composition takes the shape of its mold surface. Applying heat and pressure to something, c. removing the heat and pressure of step (b) from the thermoplastic composition; and then d. removing the thermoplastic composition molded in step (c) from its mold surface; Methods that include. 17. 17. The method of claim 16, wherein said unsaturated organic compound is maleic anhydride. 18. The polyethylene polymer grafted with the unsaturated organic compound is a high-density polymer. 18. The method of claim 17, wherein polyethylene is used. 19. The claimed ungrafted polyethylene polymer is high density polyethylene. Range 18 method. 20. Claims wherein the polyester mold surface is polyethylene terephthalate. 19 methods. 21. (i) at least one double bond in an amount of at least about 15% and at least at least about 0.01% by weight of an unsaturated organic compound containing one functional acid group; (ii) the ungrafted polyethylene polymer in an amount of Contains a polyethylene blend consisting essentially of a polyethylene polymer; a first layer, where the first layer includes polyurethane foam; The laminate is bonded to the second layer. 22. The polyethylene polymer grafted with the unsaturated organic compound is a high-density polymer. polyethylene, and the unsaturated organic compound is maleic anhydride. The laminate in box 21. 23. the ungrafted polyethylene polymer is linear low density polyethylene The laminate according to claim 22. 24. Claim 2, wherein the first layer polyethylene blend is mixed with ABS rubber. 3 laminate.