Method for curing and surface-functionalizing molded parts

Abstract

A method for curing and surface functionalization of molded parts, including processing materials that contain at least one unsaturated radically or cationically curable reactive resin system and further substances to form a molded part and cross-linking the materials up to dimensional stability during or after the processing. The method additionally includes subjecting the molded part to energetic radiation or energetic particles at least one of during the cross-linking and subsequent to the cross-linking to essentially complete curing at least of a surface region of the molded part to produce an essentially completely coatable molded part surface.

Claims

1. A method for curing and surface functionalization to produce surface-functionalized molded parts, comprising: processing at least one material of a fiber reinforced polymer material, a sheet molding compound (SMC), a bulk molding compound (BMC), and a fiber-polymer-matrix part to form a molded part; wherein the material is an unsaturated radically curable reactive resin system and further substances; and during or after the processing of the at least one material to form the molded part, partially curing the material of the molded part to dimensional stability by cross-linking, which is thermally initiated, to form a partially-cured molded part; and then subjecting the partially-cured molded part to energetic electrons in an oxygen-containing atmosphere and with a dose application in at least two treatments to essentially completely cure at least a surface region of the partially-cured molded part, to generate oxygen-containing functional groups from the atmosphere on the surface and/or in regions close to the surface of the partially-cured molded part, and to increase hydrophilicity of the surface of the partially-cured molded part, thereby producing a surface-functionalized molded part; wherein, after subjecting the partially-cured molded part to the energetic electrons in the oxygen-containing atmosphere to form the surface-functionalized molded part, gas emission from the surface of the surface-functionalized molded part, of any residual monomers, residual oligomers, or residual reactive thinning agents that remain, is virtually completely prevented, and no residual reactivity is detectable in the surface-functionalized molded part surface via differential scanning calorimetry (DSC) measurements.

2. The method of claim 1, further comprising coating the molded part such that the molded part has a coating layer during the cross-linking.

3. The method of claim 1, wherein the molded part does not include a coating layer during the cross-linking.

4. The method of claim 1, wherein the fiber reinforced polymer material is processed to form the molded part.

5. The method of claim 4, wherein the fiber reinforced polymer material comprises one of: unsaturated polyester resins; acrylic resins; and epoxy resins with a cationic initiator.

6. The method of claim 5, wherein the fiber reinforced polymer material comprises an acrylic resin, which comprises at least one of acrylates and methacrylates.

7. The method of claim 1, wherein the further substances comprise at least one of additives, fillers, reinforcing elements, further polymers, and reactive thinning agents.

8. The method of claim 1, wherein the sheet molding compound (SMC) or the bulk molding compound (BMC) is processed to form the molded part.

9. The method of claim 1, wherein processing at least one of the fiber reinforced polymer material, the sheet molding compound (SMC), the bulk molding compound (BMC), and the fiber polymer matrix part to form the molded part comprises a hot pressing.

10. The method of claim 1, wherein the oxygen-containing atmosphere is air.

11. The method of claim 1, wherein the subjecting the partially-cured molded part to the energetic electrons is carried out in combination with a plasma treatment.

12. The method of claim 1, wherein the subjecting the partially-cured molded part to the energetic electrons is carried out with doses in the range of 10 kGy to 250 kGy.

13. The method of claim 1, wherein the dose application is carried out with the same dose per treatment step.

14. The method of claim 1, wherein the dose application is carried out with a different dose per treatment step.

15. The method of claim 1, wherein the fiber-polymer-matrix part is processed to form the molded part.

16. The method of claim 1, further comprising applying a coating of paint to the surface-functionalized molded part.

17. The method of claim 1, further comprising applying a coating to the molded part at least one of prior to or subsequent to subjecting the partially-cured molded part to the energetic electrons.

18. The method of claim 17, wherein the coating is applied prior to subjecting the partially-cured molded part to the energetic electrons.

19. The method of claim 17, wherein the coating is applied subsequent to subjecting the partially-cured molded part to the energetic electrons.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) With the method according to the invention for curing and surface functionalization of molded parts, materials that contain at least one unsaturated radically or cationically curable reactive resin system and further substances, are processed to form a molded part and during or after the molding process with or without coating are cross-linked up to dimensional stability, and during the cross-linking and/or subsequently, before and/or after a coating, the molded part is subjected to a processing by energetic radiation or energetic particles up to essentially complete curing at least of the surface region of the molded part and to the production of an essentially completely coatable molded part surface.

(2) Advantageously, molded parts, which are composed of a fiber reinforced polymer material, are produced and subjected to a processing with energetic radiation or energetic particles. More advantageously the fiber reinforced polymer materials are composed of unsaturated polyester resins or acrylic resins (acrylates, methacrylates) or epoxy resins with a cationic initiator.

(3) Furthermore advantageously, an unsaturated reactive resin system is used, which contains further materials. More advantageously additives and/or fillers and/or reinforcing elements and/or further polymers and/or reactive thinning agents are used as further materials.

(4) Likewise advantageously, molded parts are used that are composed of SMC and/or BMC.

(5) And also advantageously, the molded parts are molded by hot pressing.

(6) It is also advantageous if the cross-linking is thermally initiated, wherein still more advantageously the cross-linking is carried out up to molded part stability.

(7) Furthermore, it is advantageous if the processing by energetic radiation or energetic particles is carried out in a reactive gas environment and/or in air.

(8) It is likewise advantageous if the processing by energetic electrons, gamma radiation or infrared radiation or microwave radiation or induction input is carried out in combination with a plasma treatment.

(9) And it is also advantageous if the processing is carried out exclusively with energetic electrons in a reactive gas environment and/or in air.

(10) It is also advantageous if the processing is carried out with doses in the range of 10 kGy to 250 kGy.

(11) Furthermore, it is advantageous if the dose application is carried out in at least two steps with the same dose per treatment step.

(12) It is likewise advantageous if the dose application is carried out in at least two steps with a different dose per treatment step.

(13) It is also advantageous if the processing is carried out at temperatures of 5 C. up to temperatures at which the thermal molded part stability of the materials is ensured.

(14) And it is likewise advantageous if the processing is carried out on coated fiber polymer matrix molded parts, wherein even more advantageously a painting is carried out as a coating.

(15) With the method according to the invention it is possible for the first time in a relatively short period of time and with low expenditure to obtain a molded part which is largely cured in order to prevent a leakage of low-molecular constituents, such as residual monomers, oligomers or reactive thinning agents with subsequent temperature stress during the painting process, from the SMC and BMC material, and the surface properties of which for further processing are adequate to good or very good. Cured is thereby understood as a state in which residual reactivity can no longer be detected in the component via differential scanning calorimetry (DSC) measurements. In particular this applies to coated molded parts, which can be cured according to the invention before or during or after the coating. These coated molded parts processed according to the invention exhibit good to excellent surface qualities.

(16) The method according to the invention can be applied in particular for painted SMC and BMC molded parts. Within the scope of the present invention SMC should be understood as a processable, flat semi-finished product of cross-linkable usually unsaturated polyester resins, glass fibers and necessary additives, which is processed in heated presses to form molded parts. Within the scope of the present invention BMC should be understood as an injection-moldable or transfer-moldable molding material with cut glass fibers. The fiber lengths of BMC are thereby smaller than of SMC [Liebold, R.: mo 55 (2001) p. 41].

(17) SMC and BMC molded parts are fiber polymer matrix molded parts that are produced from a reactive prepreg (resin-impregnated resin mat, SMCsheet molding compound) via thermal compression at increased temperature or bulk material (BMCbulk molding compound) via injecting molding or thermal compressing and are cross-linked up to dimensional stability. The components are produced, shaped and cross-linked according to known processes.

(18) The inventors of the present solution were able to establish that these molded parts according to the prior art within the industrial process steps and industrial process times during the thermal compression evidently do not cross-link to an adequate extent and in a reproducible manner, and a cured molded part is not subsequently obtained. The complete curing then usually only takes place in a further temperature treatment that is done in the course of the baking of the paint films. The known gas emissions and the disadvantageous effects on the paint film thereby occur.

(19) In order to avoid these disadvantageous processes, it was proposed according to the invention to carry out a curing and a surface functionalization. The curing thereby takes place according to the invention in a desired volume of the molded part. The desired volume of a molded part is essentially completely cured thereby. However, the desired volume in terms of the molded part can also relate not to the entire molded part but, for example, only one side of the molded part can be cured or only one surface region of the molded part.

(20) According to the invention, the molded parts for the curing are impinged with energetic radiation or energetic particles, which then generate excited atoms or molecules as well as ions, which preferably form radicals and induce complex chemical reactions in the molded part and/or in the desired volume of the molded part.

(21) Through the solution according to the invention, although an additional process step is introduced into the process sequence, within a short time (e.g., the cycle time of the production process) the solution according to the invention cures the molded parts such that surface defects essentially no longer occur through gas emissions and/or postcuring in the subsequent coating processes.

(22) One advantage of the solution according to the invention is that with molded parts to be coated as well as with uncoated molded parts, the gas emission of low-molecular substances, such as, for example, reactive thinning agent residues, is prevented virtually completely to completely, so that surface defects and fogging no longer occur. Fogging should be understood as referring to the emission of highly volatile substances, such as reactive thinning agent residues, for example, in the use condition of uncoated or partially coated SMC compression molded parts.

(23) It is thereby advantageous according to the invention if the processing is realized in several steps and/or with alternating application of energy per step (e.g., dose, i.e., absorbed energy per mass unit). Nevertheless, these processing times can also be fitted into the usual cycle times of the industrial production process/production lines. The applications of energy are thereby selected depending on the material composition of the molded part, its dimensions, and depending on the pressing conditions.

(24) It is also possible to carry out the curing of the molded parts only in the surface regions of the molded parts. This is advantageous in particular when large molded part thicknesses are present. The cured region has to be so thick thereby that no disadvantageous effects occur for the subsequent process steps. In particular, this cured surface region prevents materials still possibly located in the molded part, which either have not yet been cured and/or are volatile, from being able to leave the molded part, but nevertheless essentially have no negative effects on the surface of the molded part to be painted.

(25) Through the solution according to the invention a cost-effective solution has been found, with which additional refinishing can be omitted, which has been rendered possible by the thorough consideration for determining the causes.

(26) The particular advantage of the present solution lies not only in the curing of the molded parts or of volume regions or surface regions of the molded parts, but also in the fact that with the application of energy through energetic radiation or energetic particles, functional groups are also generated on the surface and/or in regions close to the surface of the molded parts, which lead to a better adhesion of the coating and an increase of the hydrophilicity of the surface. In this manner an improvement of the surface quality of the molded part surface, and thus, also of the painted/coated molded parts is ultimately also obtained.

(27) The invention is explained in more detail below based on several exemplary embodiments.

Example 1

(28) An automobile molded part is produced from a prepreg of a low-profile formula SMC paste:

(29) TABLE-US-00001 Unsaturated polyester resin 60 pbw (60% by weight in styrene) Low-profile additive 40 pbw (40% by weight in styrene) Calcium carbonate 10 pbw t-butyl peroxybenzoate 1.5 bpw Zinc stearate 4 pbw Magnesium oxide 1 pbw SMC prepreg: SMC paste 75% by weight Glass fibers 25% by weight (cut, length: 1 inch)
under the following conditions via thermal pressing:
Temperature/female die: 140 C.; temperature/male die: 139 C., closing time: 12 s, pressing time: 180 s; compacting pressure: 14 MPa.
The residual reactivity in the molded part determined via DSC is 8 J/g based on the initial reactivity of the prepreg of 40 J/g.

(30) Subsequently, the molded part is irradiated by electrons with a dose of 140 kGy in air atmosphere at a product speed of 0.3 m/minute. The irradiation takes place in the process sequence between the ejection of the molded part from the press and the subsequent processing steps. Thereafter residual reactivity can no longer be detected in the molded part by DSC and the molded part is thus completely cured. The wetting contact angle with water as test liquid drops from 98 to 78 as a result of the incorporation of oxygen-containing groups into the surface.

Example 2

(31) A commercial vehicle molded part is produced from a prepreg of a low-profile formula under the following conditions by thermal pressing:

(32) Temperature/female die: 140 C.; temperature/male die: 139 C., closing time: 12 s, pressing time: 180 s; compacting pressure: 14 MPa.

(33) The residual reactivity determined in the molded part via DSC is 7 J/g based on the initial reactivity of the prepreg of 37 J/g.

(34) Subsequently, the molded part is irradiated by electrons with individual doses of 720 kGy at a product speed of 2.1 m/minute under air atmosphere. The irradiation is carried out in the process sequence between the ejection of the molded part from the press and the subsequent processing steps. Thereafter residual reactivity can no longer be detected in the molded part by DSC and the molded part is completely cured. The wetting contact angle with water as test liquid drops from 100 to 32 as a result of the incorporation of oxygen-containing groups into the surface.

Example 3

(35) An automobile molded part is produced from a prepreg of a low-shrink formula (see above)

(36) TABLE-US-00002 Unsaturated polyester resin 16.4% by weight (70% by weight in styrene) Polystyrene 11% by weight (40% by weight in styrene) Para-t-butyl peroxybenzoate 0.3% by weight Zinc stearate 0.7% by weight Calcium carbonate 41.1% by weight Magnesium oxide 0.5% by weight Glass-fiber roving 30% by weight (cut, 1 inch length)
under the following conditions via thermal pressing:
Temperature/female die: 140 C.; temperature/male die: 139 C., closing time: 12 s, pressing time: 180 s; compacting pressure: 14 MPa.
The residual reactivity in the molded part determined by DSC is 2.2 J/g based on the initial reactivity of the prepreg of 24 J/g.

(37) Subsequently, the component is completely cured via electron irradiation with 70 kGy at product transport speeds of 0.6 m/minute and subsequently with 710 kGy at a product speed of 4.2 m/minute under air atmosphere. Thereafter residual reactivity can no longer be established in the component by DSC. The wetting contact angle with water as test liquid drops from 95 to 72 as a result of the incorporation of oxygen-containing groups into the surface. The roughness is in a comparable range to the state after the pressing process.

Example 4

(38) An automobile molded part is produced from an SMC prepreg of an automotive class A formula under the following conditions via thermal pressing:

(39) Temperature/female die: 150 C.; temperature/male die: 145 C., closing time 10 s, pressing time: 160 s; compacting pressure 12 MPa.

(40) The residual reactivity in the molded part determined via DSC is 17% on average depending on the thickness based on the initial reactivity of the prepreg of 41 J/g. With a component thickness 2.2-3.2 mm a residual reactivity between 14 and 20%, with 5.4 mm of 13% and with 10.3 mm of 10% of the initial reactivity of the prepreg was thereby determined.

(41) Subsequently, the molded part is irradiated by electrons with individual doses of 1210 kGy at a product speed of 4.2 m/minute under air atmosphere. The irradiation takes place in the process sequence between the ejection of the molded part from the press and the following processing step. Thereafter residual reactivity can no longer be detected in the molded part by DSC and the molded part is completely cured. The wetting contact angle with water as test liquid drops from 95 to 72 as a result of the incorporation of oxygen-containing groups into the surface.