CA2108681A1 - Plastisols which prevent the yellowing of top coats, process for their preparation and their use - Google Patents

Plastisols which prevent the yellowing of top coats, process for their preparation and their use

Info

Publication number
CA2108681A1
CA2108681A1 CA002108681A CA2108681A CA2108681A1 CA 2108681 A1 CA2108681 A1 CA 2108681A1 CA 002108681 A CA002108681 A CA 002108681A CA 2108681 A CA2108681 A CA 2108681A CA 2108681 A1 CA2108681 A1 CA 2108681A1
Authority
CA
Canada
Prior art keywords
plastisol
additive
plastisols
derivatives
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002108681A
Other languages
French (fr)
Inventor
Bernhard Koesters
Xaver Muenz
Manfred Asang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Teroson GmbH
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2108681A1 publication Critical patent/CA2108681A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/07Aldehydes; Ketones
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Medicinal Preparation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Abstract The invention relates to plastisols which prevent a yellowing of top coats applied thereon, to a process for their preparation and to their use. The plastisols based on PVC or methacryl contain, in addition to basic adhesion promoters, aldehydes, ketones, their derivatives, oligomers or mixtures of same.

Description

210868~

lastisols which ~revent the Yellowina of to~ coats. ~rocess for their Dre~aration and their use The invention relates to plastisols which prevent yellowing of top coats applied thereon, to a process for their preparation and their use .

Plastisols are used in the car industry for undersealing and for seam-closing and sealing. Depending on the application aim, further aggregates are added to the plastisols, which are dispersions of fine polymer particles in liquid plasticizers. Such aggregates are flow-improvers, stabilizers, adhesion promoters, fillers and water-absorbing substances. Adhesion promoters are added to the plasti-8018 to produce long-life adhesion of the plastisols to steel or galvanized, tin-plated or electro-dip coated steel sheets. As ad-hesion promoters for PVC plastisols, basic compounds such as poly-aminoamides (PAA) are used, for example. In contrast, as adhesion promoters for polymethacrylic plastisols, usually basic vinyl ~midazoles are used, to which polyaminoamides are optionally added additional adhesion promoter component. The other aqgregates are likewise often basic compounds, e.g. calcium oxide, barium oxide and calcium carbonate. With the final coating, the plastisols are coated over at the same time.

Since electro-dip coats, particularly cathodic electro-dip coats are used for pr~m~ng steel parts and sheets, it is observed that the eoats applied to the plastisols yellow with time. Thl~ problem partlcularly affect~ light, pastel-coloured and white coats, be-e~u-- with the-- the di~coloratlon is more easily noticed, parti-eularly if they are applied without an intermediate coat (filler).
llowinq is espeeially serious with white coats. Yellowing does not in most ca~es appear ~mo~ately after stoving of the top eo~ting, but only after some time. This is not a question of a
- 2 - 2~08~8~

yellowing of the plastisol itself, which could possibly appear through the top-coat layer, but of a gradual discoloration of the top coat itself.

To solve this problem, it was proposed in DE-A-38 21 926 to add as additives to the plastisols acid cation exchangers, whose effect is seen in that upon stoving they bind liberated amines. The addition of acid substances however has the disadvantage tha~ they reduce or even inhibit the effect of basic adhesion promoters. Further, acid components react with other basic substances optionally present in the plastisol such as calcium oxide and chalk, so that carbon di-oxide and water form and the plastigels formed from the plastisols become porous.

The aim of the invention is to prevent the yellowing of a top coat which i9 applied to steel parts or metal sheets which have been primed with an electro-dip coat and treated with plastisols, either with or without an intermediate coat, without having to use acid plastisol aggregates.

This aim i8 achieved with plastisols which, in addition to basic adhesion promoters, and as further additive contain simple alde-hydes, ketones, their derivatives, oligomers or mixtures of same.

Preferred embodiments of the invention are the sub~ect of the sub-~idiary claims.

Partlcularly ~uitable as yellowing-inhibiting additlve are ali-phatlc monoaldehydes ~uch aJ formaldehyde, acetaldehyde and pro-pionaldohyde or simple aromatic aldehydes and ketones such as ben~aldehyde, benzophenone or benzoquinone a8 well a8 their deri-vatlve~. Re~amethylenetetramine ~urotropin or 1,3,5,7-tetra-aza-adamantane)~ which splits off formaldehyde under the said condi-_ 3 _ 2108~

tions, has proved especially effective. However, al~o suitable arefor example di-, tri- or tetramers (oligomers) of the aldehydes such as trioxymethylene (1,3,5-trioxane), paraldehyde (2,4,6-tri-methyl-1,3,5-trioxane) or metaldehyde (a tetramer of acetalaldehyde (C2H~O)~) -The plastisols according to the invention already have a yellowing-inhibiting effect from a content of approximately 0.001 % of "anti-yellowing additive~. Preferably, the content of this additive is 0.05 to 5 %, a content of 0.1 to 3 % being especially preferred.

The yellowing-inhibiting effect becomes especially clear if, in addition to the basic polyaminoamides usable for example as adhesion promoter, several of the other basic aggregates are present in the plastisol in relatively large amounts. Advanta-geously the plastisols also contain only basic adhesion promoter components. But even if these basic components are reduced to the e~tent that is still ~ust necessary, no discoloration takes place under very unfavourable circumstances (thick-layer electro-dip coat$ng, warm, very humid atmosphere etc.) in the presence of the yellowing-inhibiting addltive.

It is assumed that the yellowing substance is a basic compound which could be captured with acid compounds. However, the use of acid additive~ is to be avoided. Through the aldehyde or ketone, ~hich optionally must first be released from a derivative, the concentration of the yellowing basic substance is presumably lowered at least until yellowing is no longer observable.

Of cour~e, the pla~ti~ol can also contain other additives whose if-ct~ are not ~mpaired by the anti-yellowinq additive.

_ 4 _ 2~0868~

During preparation of the plastisol the yellowing-inhibiting addi-tive is mixed in together with the other additives to be incorpo-rated. The individual additives, however, can also be individually made into a paste for example with the liquid plasticizer prior to mixing to form the plastisol compound and added to the plastisol in this form.

Embodiment~: ~lasti~ols PVC ~lastisols A~ A~ B. Bb PVC homopolymer 20 20 30 30 (K value 70) Plasticizer (DINP) 30 30 35 35 Thinner 5 5 _ _ (white spirit 180/210) Filler (chalk) 43 44 29 30 C~O -- -- 1 1 TiO2 - - 2 2 SiO2 - - 0.5 0.5 Ba~ic lead sulphate - - O.5 0.5 Adhe~ion promoter (PAA) Urotropin 1 - 1 -_ 5 _ 210868~

AcrYlate Dlastisols:
C~ Cb Poly-MNA/BMA with 2 % vinyl imidazole 30 30 Cha~k 29.2 28.9 CaO
Urotropin 0.3 MMA = methyl methacrylate; BMA = butyl methacrylate Pre w ration method~:

1. PVC plastisol A~ with all components directly mixed as one-pot process.
PVC plastisol A~ without urotropin likewise.
2. PVC plastisol A~: urotropin is dispersed in plasticizer, finely abraded on a roll and then added to the plastisol.
3. PVC plastisol B. ~in the case of Eb without urotropin)s mix all solid additives (CaC03, CaO, TiO2 etc + urotropin) with a little plasticizer, abrade and finally add the rest, i.e. PAA
and polymers.
4. Acrylic plastisols (C, and Cb) as 1.

During vehicle construction, after the sheets have been coated with ~n electro-dip coat and treated with plastisol, 8ay at occurring weld ~eams, they are provided with a top coat. This coat is subse-quently stovod.

For example, plastisol i8 applied to the sheets coated with elec-tro-dip coat to achleve the effect according to the invention and ~ad- to qel at 140 C for 30 minute~. Then, optionally, filler - 6 - 210868~

coats are sprayed onto the sheet and onto the plastisol, ventilated for 10 minutes and stoved at 130 oc. Subsequently the top coat is sprayed on, dried for 10 minutes and stoved for 20 minutes at 130C.

To speed up determination of the degree of yellowin~ occurring with sheets thus treated, test sheets were manufactured.

1. Pretreatment of the test sheets 2. Electro-dip coat coated sheets are laid on top of each other, a distance of 1 mm between them being maintained with the aid of interspersed spheres. The sheets are ~ecurely wrapped in aluminium foil to maintain high condensate concentrations on the inner surfaces of both sheets during the following 30 minute heat treatment at 180 oc. After cooling down, the aluminium foil is removed and to better determine the effect of the electro-dip coat a strip of 10 to 20 mm of the electro-dip coat is removed from the centre of the sheet.
3. ~anufacture of the test sheets The plastisol is applied as a bead, 0 to 4 mm high and 50 mm long, to the inner side of the test sheet. Afterwards, the plastisol is cro~slinked at the necessary temperature. The white top coat is sprayed in a thickness of 30 to 40 ~m onto the cooled sheet and cured under the necessary stoving conditions (see Figure 1.).
4. Storage condltions The test sheets are suspended in a securely closed box, whose ba~e i~ covered wlth water (water depth 10 to 20 mm). The box i~ ~tored at 60 C.
S. Evaluatlon Accordlng to guallty, the flrst result~ can be obtained after everal hours, days or a few weeks.

_ 7 _ 210868~

The yellowing of the sheets is rated in each case with values of O
to 10, 0 ~ignifying a complete yellowing and 10 virtually no yellowing.

Test results:

Plast~ol Prepared Tested No. ~s per asper lea~ng Rating Appraisal ql~iclc at room after s days method temp.

l)A, 1 ~ 2 10 2)A~ 1 ~ 2 4 3)A, 1 ~c 6 10 4~Ab 1 ~c 6 2 S)A~ 2 ~ 2 10 6)u~, 2 s 6 10 ~ 3 s 8 10 83~ 3 s 8 7 9)~, 3 s 40 10 3 s 40 2 ll)B. 1 s 6 10 lZ~, 1 s 6 3 ~3)C, 4 s 6 10 ~4)S 4 s 6 2 The formulation with b i8 alway~ prepared without urotropin.

- 8 - 210868~

The results that can be seen from the Table clearly show that the plastisols to which an anti-yellowing additive was added are supe-rior to the conventional pla~tisols in terms of the yellowing phe-nomenon. Even after relatively long weathering, no discoloration is di~cernible.

The invention further comprises a process for preparing the plasti-~ols according to the invention and their use on steel part~ and ~heets primed with electro-dip coat.

Claims (18)

Patent claims
1. Plastisol characterized in that it contains only basic adhesion promoter components and, as further additive, simple aldehydes, ketones, their derivatives, oligomers or mixtures of same.
2. Plastisol according to claim 1, characterized in that the additive in the plastisol is contained in a quantity of more than 0.001 wt-% relative to the total plastisol.
3. Plastisol according to any of claims 1 or 2, characterized in that the content of this additive is 0.05 to 5 wt-%, particu-larly 0.05 to 3 wt-%.
4. Plastisol according to any of claims 1 to 3, characterized in that plastisols based on PVC or polymethacryl are involved.
5. Plastisol according to any of claims 1 to 4, characterized in that it contains, as adhesion promoter, polyaminoamides and/or vinyl imidazoles.
6. Plastisol according to any of claims 1 to 5, characterized in that, as additive, simple monoaldehydes, ketones, their derivatives, oligomers or mixtures of same are present.
7. Plastisol according to any of claims 1 to 6, characterized in that the additive is formaldehyde, acetaldehyde, propionalde-hyde and their derivatives or oligomers.
8. Plastisol according to any of claims 1 to 7, characterized in that the additive is hexamethylenetetramine.
9. Plastisol according to any of claims 1 to 8, characterized in that the plastisol contains other usual aggregates.
10. Process for preparing plastisols according to any of claims 1 to 9, characterized in that the yellowing-inhibiting additive, together with the other additives to be incorporated, is mixed into the plastisol compound or the individual additives are individually made into a paste with the plasticizer prior to mixing with the plastisol compound and added to the plastisol compound in this form.
11. Use of plastisols which, in addition to basic adhesion promoters, contain aldehydes, ketones, their derivatives or mixtures of same as additive, on steel parts or sheets primed with electro-dip coats, which steel parts or sheets are subsequently coated over.
12. Use according to claim 11, characterized in that the additive in the plastisol is contained in a quantity of more than 0.001 wt-% relative to the total plastisol.
13. Use according to any of claims 11 or 12, characterized in that the content of the additive is 0.05 to 5 wt-%, particularly 0.05 to 3 wt-%.
14. Use according to any of claims 11 to 13, characterized in that plastisols based on PVC or polymethacryl are involved.
15. Use according to any of claims 11 to 14, characterized in that polyaminoamides and/or vinyl imidazoles are used as adhesion promoter.
16. Use according to any of claims 11 to 15, characterized in that the additive is monoaldehydes and monoketones, particularly formaldehyde, acetaldehyde, propionaldehyde and their derivatives or oligomers.
17. Use according to any of claims 11 to 16, characterized in that hexamethylenetetramine is used as additive.
18. Use according to any of claims 11 to 17, characterized in that the plastisols contain further usual aggregates.
CA002108681A 1991-04-19 1992-04-17 Plastisols which prevent the yellowing of top coats, process for their preparation and their use Abandoned CA2108681A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4112823.0 1991-04-19
DE4112823A DE4112823C2 (en) 1991-04-19 1991-04-19 Yellowing of topcoats preventing plastisols, process for their preparation and their use

Publications (1)

Publication Number Publication Date
CA2108681A1 true CA2108681A1 (en) 1992-10-20

Family

ID=6429942

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002108681A Abandoned CA2108681A1 (en) 1991-04-19 1992-04-17 Plastisols which prevent the yellowing of top coats, process for their preparation and their use

Country Status (7)

Country Link
EP (1) EP0580697B1 (en)
JP (1) JPH06506710A (en)
AT (1) ATE185824T1 (en)
CA (1) CA2108681A1 (en)
DE (2) DE4112823C2 (en)
ES (1) ES2138598T3 (en)
WO (1) WO1992018565A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4438959A1 (en) * 1994-10-31 1996-05-02 Schaeffler Waelzlager Kg Mechanical valve tappet for internal combustion engine

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2654871C3 (en) * 1976-12-03 1984-10-04 Schering AG, 1000 Berlin und 4709 Bergkamen Polyvinyl chloride plastisols with improved adhesion
DE2840996C2 (en) * 1978-09-21 1984-05-03 Teroson Gmbh, 6900 Heidelberg Process for the production of plastisols
DE3403497A1 (en) * 1984-02-02 1985-08-08 Bayer Ag, 5090 Leverkusen ADHESIVE ADDITIVES CONTAINING PVC PLASTISOLS FOR COATING PURPOSES AND THEIR USE
DE3821926A1 (en) * 1988-06-29 1990-02-22 Ems Togo Ag PLASTISOL MOLDING, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
US4900771A (en) * 1989-01-26 1990-02-13 Aster, Inc. Hot applied plastisol compositions

Also Published As

Publication number Publication date
EP0580697A1 (en) 1994-02-02
WO1992018565A1 (en) 1992-10-29
ES2138598T3 (en) 2000-01-16
ATE185824T1 (en) 1999-11-15
EP0580697B1 (en) 1999-10-20
JPH06506710A (en) 1994-07-28
DE59209761D1 (en) 1999-11-25
DE4112823C2 (en) 1996-11-21
DE4112823A1 (en) 1992-10-22

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Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued