HEAT COMPOSITE SYSTEM BASED ON POLYURETHANE RIGID FOAM FOR BUILDING FACADES

Abstract

The present invention relates to a process for the production of a composite element. The process includes (i) provision of an outer layer with an uncoated surface and a coated surface coated at least partially with a composition (B) including at least one inorganic material, (ii) treatment of the uncoated surface of the outer layer and (iii) application, to the treated surface of the outer layer, of a composition (Z2) suitable for the production of a polyurethane foam and/or polyisocyanurate foam. The present invention further relates to a composite element obtainable or obtained by a process of the invention, and also to the use of a composite element obtainable or obtained by a process of the invention or of a composite element of the invention as insulation material or in the construction of faades.

Claims

1. A process for the production of a composite element, the process comprising: i) provision of an outer layer with an uncoated surface and a coated surface coated at least partially with a composition (B) comprising at least one inorganic material; ii) treatment of the uncoated surface of the outer layer; and iii) application, to the outer-layer surface treated in step ii), of a composition (Z2) suitable for the production of a polyurethane foam and/or polyisocyanurate foam, wherein the composition (B) has coated at least 50% of the coated surface of the outer layer, and wherein the composition (B) comprises from 70 to 95% by weight of a pulverulent inorganic material and from 5 to 30% by weight of a binder, based in each case on the entire composition (B), and wherein the outer layer is impermeable to diffusion.

2. The process according to claim 1, wherein the treatment in step ii) is selected from the group consisting of corona treatment, plasma treatment, flame treatment, and application of a composition (Z1) comprising at least one adhesion promoter.

3. The process according to claim 1, wherein the treatment in step ii) comprises application of a composition (Z1) comprising at least one adhesion promoter.

4. The process according to claim 1, wherein the composition (B) has coated at least 75% of the coated surface of the outer layer.

5. The process according to claim 1, wherein the outer layer has a plurality of sublayers.

6. The process according to claim 1, wherein the outer layer comprises a plastics foil that is impermeable to diffusion or a metal foil.

7. The process according to claim 1, wherein the thickness of the at least partially coated outer layer is from 0.01 mm to 5.0 mm.

8. The process according to claim 2, wherein the adhesion promoter is one of a compound reactive toward isocyanates and a polyisocyanate prepolymer.

9. The process according to claim 8, wherein the compound reactive toward isocyanates is selected from the group consisting of compounds having OH functional groups, compounds having NH functional groups, and compounds having SH functional groups.

10. The process according to claim 8, wherein the compound reactive toward isocyanates is selected from the group consisting of polyethers, polyesters, compounds bearing ester and ether groups, compounds bearing urethane and ester groups, compounds bearing urethane and ether groups, compounds bearing urethane, ester, and ether groups, and compounds bearing urethane groups.

11. The process according to claim 2, wherein the composition (Z1) comprises at least one compound reactive toward isocyanates and comprises at least one polyisocyanate.

12. The process according to claim 1, wherein the composition (Z2) comprises at least one polyisocyanate and comprises at least one compound reactive toward isocyanates.

13. The process according to claim 1, wherein the composition (Z2) comprises: a) at least one polyisocyanate; b) at least one compound reactive toward isocyanates; and c) at least one blowing agent.

14. The process according to claim 2, wherein the composition (Z1) comprises at least one additive which improves compatibility between the uncoated surface of the outer layer and the composition (Z1).

15. The process according to claim 2, wherein the composition (Z1) is applied to the outer layer by means of spray-application or rolling.

16. The process according to claim 1, wherein the process comprises a step iv): iv) application of an outer layer to the layer applied in step iii).

17. A composite element obtainable by the process according to claim 1.

18. An insulation material comprising the composite element of claim 17.

19. A material for use in construction of faades comprising the composite element of claim 17.

Description

EXAMPLES

I. Production Example

[0210] An overhead mixer was used to foam polymeric MDI with isocyanate-reactive components, blowing agents, catalysts and all the other additional substances in a beaker, and the product was charged to a box mold (20208 cm.sup.3) controlled to a temperature of 60 C. and equipped with outer layer (vliepatex WDVS DD, thickness about 0.5 mm, barrier foil facing toward the reaction mixture) above and below; after input of the reaction mixture, the mold was closed in order to obtain a foam with outer layer applied above and below.

[0211] The following polyol component was used in all of the experiments:

[0212] 61 parts by weight of polyesterol composed of the esterification product of terephthalic acid, glycerol, diethylene glycol and oleic acid.

[0213] 8 parts by weight of polyetherol made of ethoxylated ethylene glycol with hydroxy functionality 2 and hydroxy number 190 mg/KOH/g.

[0214] 27.5 parts by weight of trichloroisopropyl phosphate (TCPP) flame retardant.

[0215] 2.5 parts by weight of Tegostab B8498 (silicone-containing stabilizer from Evonik).

[0216] 2.7 parts by weight of water.

[0217] 0.8 part by weight of dipropylene glycol.

[0218] Additional substances:

[0219] 15 parts by weight of 70:30 cyclopentane/pentane.

[0220] 2 parts by weight of potassium acetate solution (47% by weight of ethylene glycol).

[0221] also bis(2-dimethylaminoethyl) ether solution (33% by weight in dipropylene glycol) to adjust fiber times.

[0222] Isocyanate component:

[0223] A quantity of Lupranat M50 (polymeric methylenediphenyl diisocyanate (PMDI) with viscosity about 500 mPa*s at 25 C. from BASF SE) sufficient to achieve an index of 280. Isocyanate component and polyol component were used in a ratio by weight of 206:100.

[0224] The quantity of reaction mixture in the box mold was selected to give a foam of envelope density 33 +/2 g/l. Fiber time was moreover adjusted to 47 +/2 s by varying the proportion of the bis(2-dimethylaminoethyl) ether solution (33% by weight in dipropylene glycol).

[0225] The lower outer layer on which the reaction mixture was applied was directly treated in the following manner directly before placing in the box mold:

Comparative Example

[0226] No pretreatment

Inventive Example 1

[0227] Application of a polyetherol made of propoxylated propylene glycol with hydroxy functionality 2 and hydroxy number 28 mg KOH/g; a manual coater was used here to apply the polyetherol in a layer thickness of 250 m.

Inventive Example 2

[0228] Application of a polyetherol made of sequentially ethoxylated and propoxylated glycerol with hydroxy functionality 3 and hydroxy number 160 mg KOH/g; a manual coater was used here to apply the polyetherol in a layer thickness of 250 m.

Inventive Example 3

[0229] Application of a polyetherol made of ethoxylated glycerol with hydroxy functionality 3 and hydroxy number 540 mg KOH/g; a manual coater was used here to apply the polyetherol in a layer thickness of 250 m.

Inventive Example 4

[0230] Application of a polyetherol made of castor oil with hydroxy functionality 3 and hydroxy number 160 mg KOH/g; a manual coater was used here to apply the polyetherol in a layer thickness of 250 m.

Inventive Example 5

[0231] Application of a polyetherol made of sequentially ethoxylated and propoxylated glycerol with hydroxy functionality 3 and hydroxy number 160 mg KOH/g comprising 5% by weight of oleic acid; a manual coater was used here to apply the polyetherol in a layer thickness of 250 m.

Inventive Example 6

[0232] Application of a prepolymer made of propoxylated propylene glycol with hydroxy functionality 2 and hydroxy number 28 mg KOH/g and Lupranat M20 (polymeric methylenediphenyl diisocyanate (PMDI) with viscosity about 200 mPa*s at 25 C. from BASF SE), NCO content of the prepolymer being 15%; a manual coater was used here to apply the prepolymer in a layer thickness of 250 m.

Inventive Example 7

[0233] Application of a prepolymer made of sequentially ethoxylated and propoxylated propylene glycol with hydroxy functionality 2 and hydroxy number 30 mg KOH/g and Lupranat M20 (polymeric methylenediphenyl diisocyanate (PMDI) with viscosity about 200 mPa*s at 25 C. from BASF SE), NCO content of the prepolymer being 15%; a manual coater was used here to apply the prepolymer in a layer thickness of 250 m.

Inventive Example 8

[0234] Application of a prepolymer made of sequentially ethoxylated and propoxylated propylene glycol with hydroxy functionality 2 and hydroxy number 30 mg KOH/g and Lupranat M20 (polymeric methylenediphenyl diisocyanate (PMDI) with viscosity about 200 mPa*s at 25 C. from BASF SE), NCO content of the prepolymer being 10%; a manual coater was used here to apply the prepolymer in a layer thickness of 250 m.

Inventive Example 9

[0235] Application of a prepolymer made of sequentially ethoxylated and propoxylated propylene glycol with hydroxy functionality 2 and hydroxy number 30 mg KOH/g and Lupranat M20 (polymeric methylenediphenyl diisocyanate (PMDI) with viscosity about 200 mPa*s at 25 C. from BASF SE), NCO content of the prepolymer being 20%; a manual coater was used here to apply the prepolymer in a layer thickness of 250 m.

[0236] After production of the samples, they were stored for 24 hours at room temperature (from 18 to 22 C.). The following were then determined: peel strength in accordance with the general test specification A as described below, based on VW PV 2034, and tensile strength in accordance with DIN 53292/DIN EN ISO 527-1. In each case three specimens were tested and the average was calculated. The stability of the film produced prior to foaming on the lower outer layer was moreover evaluated qualitatively.

[0237] Good film quality was indicated by stability for at least 30 s, where this means that no holes developed in the film that would have led to inhomogeneous covering of the outer layer and could have had an adverse effect on adhesion of the foam on the outer layer. Table 1 collates the results.

TABLE-US-00001 TABLE 1 Tensile bond strength Peel strength Film [N/mm.sup.2] [N/5 cm] quality Comparative example 0.04 +/ 0.02 3.5 +/ 1.6 no film Inventive example 1 0.11 +/ 0.02 12 +/ 2 good Inventive example 2 0.07 +/ 0.02 13 +/ 4 poor Inventive example 3 0.05 +/ 0.03 6.1 +/ 0.9 very poor Inventive example 4 0.13 +/ 0.04 9.4 +/ 1.6 good Inventive example 5 0.13 +/ 0.01 10.1 +/ 1.3 moderate Inventive example 6 0.16 +/ 0.02 22 +/ 2 good Inventive example 7 0.15 +/ 0.02 28 +/ 5 good Inventive example 8 0.12 +/ 0.02 27 +/ 12 good Inventive example 9 0.12 +/ 0.02 18.4 +/ 1.8 good

II. Production Example/Testing of Composites

[0238] Rigid PIR foam sheets were produced from a commercially obtainable PIR formulation (Elastopir) in a twin-belt system by a continuous process conventionally used in the industry. The thickness of the rigid PIR foam sheets was 100 mm, with density from 30 to 31 g/l. The following outer layer variants were used: [0239] Vliepatex WDVS DD outer layer on upper side and lower side (foil composite impermeable to diffusion with single-side inorganic coating, thickness about 0.5 mm, barrier layer facing toward the insulation material) [0240] Vliepatex WDVS DD outer layer on upper side and lower side; application of a two-component adhesion promoter to the lower outer layer prior to application of the PIR reaction mixture (spinning disk) [0241] commercially available aluminum outer layer (50 m, also termed alu below) on upper side and lower side [0242] commercially available aluminum outer layer (50 m) on upper side and lower side; application of a two-component adhesion promoter to the lower outer layer prior to application of the PIR reaction mixture (spinning disk)

[0243] The sheets were then subjected to a tensile bond strength test based upon the Guideline for European Technical Approvals for external composite thermal insulation systems with rendering (ETAG 004, section 5.1.4.1): The lower side of the insulation sheets was coated with mortar (Heck K+A, dry ready-mix mortar in accordance with DIN 18350) and then stored for seven days at 23 C. and 50% rel. humidity and 21 days at 23 C. in water. An angle grinder was used to make cuts through the mortar and the outer layer, extending just into the insulation material, thus giving six squares measuring 5050 mm. An adhesive was used to fix square metal sheets measuring 5050 mm on the cut-out areas. The tensile bond strength of the insulation-material-outer-layer-mortar composite was then measured (F 20 DEASY M 2000, class 1 tester with official calibration, test velocity 125 N/s with no preloading). For composite thermal insulation systems the Guideline requires an average minimal tensile bond strength of 0.08 N/mm.sup.2 or fracture within the insulation material.

TABLE-US-00002 TABLE 2 Measured Adequate in Outer Adhesion value accordance Sample layer promoter (AP) Failure [N/mm.sup.2] with ETAG 004 1.1 Vliepatex no AP interface 0.070 WDVS DD 1.2 Vliepatex no AP interface 0.060 WDVS DD 1.3 Vliepatex no AP interface 0.040 WDVS DD 1.4 Vliepatex no AP interface 0.041 WDVS DD 1.5 Vliepatex no AP interface 0.046 WDVS DD 1.6 Vliepatex no AP interface 0.042 WDVS DD 1 Vliepatex no AP 0.050 0.012 No (Average) WDVS DD 2.1 Vliepatex with AP interface 0.096 WDVS DD 2.2 Vliepatex with AP interface 0.084 WDVS DD 2.3 Vliepatex with AP coating 0.110 WDVS DD 2.4 Vliepatex with AP coating 0.082 WDVS DD 2.5 Vliepatex with AP interface 0.092 WDVS DD 2.6 Vliepatex with AP insulation 0.074 WDVS DD material 2 Vliepatex with AP 0.090 0.013 yes (Average) WDVS DD 3.1 Alu no AP interface 0.005 3.2 Alu no AP interface 3.3 Alu no AP interface 0.006 3.4 Alu no AP interface 0.003 3.5 Alu no AP interface 0.003 3.6 Alu no AP interface 0.005 3 Alu no AP 0.004 0.001 no (Average) 4.1 Alu with AP interface 0.004 4.2 Alu with AP interface 0.005 4.3 Alu with AP interface 0.005 4.4 Alu with AP interface 0.002 4.5 Alu with AP interface 0.005 4.6 Alu with AP interface 0.006 4 Alu with AP 0.005 0.001 no (Average)

[0244] The minimal value required by the composite thermal insulation systems standard: 0.08 N/mm.sup.2 or fracture within the insulation material is achieved only with adhesion promoter and Vliepatex WDVS DD outer layer.

III. Test Specification A for Determination of Peel Strength: Roller Peel Test Based on VW PV 2034

[0245] A longitudinal section of about 50 mm of the adhering outer layer of a sample measuring 17050 mm cut from a composite element was released from the substrate material. The sample is inserted into a floating-roller unit (two rollers, diameter 20 mm, length about 57 mm, separation 6 mm) clamped into the upper clamping jaw of a universal tester (UT). The flexible released end section is passed downward between the rollers at an angle of 90 and fixed in the lower clamp of the UT. Once the pretensioning force has reached 4 N, the flexible material is peeled from the substrate material at an angle of 90 (roller) at a test velocity of 50 mm/min.

[0246] The test continues for 100 mm and is then terminated. Six reference forces are determined at intervals of 10 mm at test positions between 25 mm and 75 mm. The peel force is calculated from the average of these six reference forces and is stated in N/5 cm.