阅读说明：本技术 潜在反应性胶粘剂配制品 (Latent reactive adhesive formulations ) 是由 J·布希纳 H-J·拉斯 H·克劳斯 M·梅尔基奥尔 于 2020-04-17 设计创作，主要内容包括：本发明涉及具有>+30℃的软化温度的固体聚碳二亚胺树脂作为胶粘剂分散体聚合物的交联剂的用途。至少一种固体聚碳二亚胺树脂和至少一种聚合物分散体的混合物适用于生产储存稳定的潜在反应性胶粘剂分散体、潜在反应性胶粘剂层、自支撑潜在反应性胶粘剂膜或潜在反应性胶粘剂粉末。(The invention relates to the use of solid polycarbodiimide resins having a softening temperature of > +30 ℃ as crosslinking agents for adhesive dispersion polymers. The mixture of at least one solid polycarbodiimide resin and at least one polymer dispersion is suitable for producing a storage-stable latent reactive adhesive dispersion, a latent reactive adhesive layer, a self-supporting latent reactive adhesive film or a latent reactive adhesive powder.)

1. Formulations based on latent reactivity of dispersion polymers having a minimum film-forming temperature of ≦ 23 ℃ and a glass transition temperature of ≦ 0 ℃ measured by DSC (heating rate 20K/min), which may be crosslinked with carbodiimide and comprise at least one polycarbodiimide having a glass transition temperature of at least +30 ℃ and an average functionality of at least 2.

2. Formulation as claimed in claim 1, characterized in that it is an aqueous dispersion.

3. Formulation as claimed in claim 1, characterized in that it is a pulverulent mixture.

4. Formulation as claimed in claim 1, characterized in that it is a film.

5. Formulation as claimed in claims 1 to 4, characterized in that the polycarbodiimide has aliphatically or cycloaliphatically attached carbodiimide groups.

6. A formulation as claimed in claims 1 to 5, characterized in that the polycarbodiimide has particles of a particle size dv (50) ≦ 70 μm, preferably dv (50) ≦ 20 μm, particularly preferably having dv (50) ≦ 3.4 μm.

7. Formulation as claimed in claims 1 to 6, characterized in that the dispersion polymer is a polyurethane polymer or a polyurethane-polyurea polymer.

8. Formulation as claimed in claims 1 to 7, characterized in that the dispersion polymer is a partially crystalline polyurethane polymer or polyurethane-polyurea polymer.

9. Formulation according to claims 1 to 8, characterized in that the dispersion polymer is a polyurethane polymer or polyurethane-polyurea polymer comprising polycarbonate segments in the polyol component (A).

10. Substrates coated with the formulations as claimed in claims 1 to 4.

11. Use of the formulation as claimed in claims 1 to 9 as an adhesive.

12. Use of the formulation as claimed in claims 1 to 2 as an adhesive dispersion.

13. Use of a formulation as claimed in claims 1 to 9 for the manufacture of a storage-stable latent reactive adhesive layer.

14. Use of a formulation as claimed in claims 1 to 9 for the manufacture of a storage-stable self-supporting latent reactive adhesive film.

15. Use of the formulation as claimed in claims 1 to 9 for the manufacture of storage-stable self-supporting latent-reactive adhesive powders.

16. Substrate coated with a potentially reactive film obtained from the formulation as claimed in claims 1 to 9.

17. A substrate that is glued by heat-induced curing of a latent reactive film on a substrate coated therewith as claimed in claim 17.

examples

The invention is further illustrated by, but not limited to, the following examples.

Raw materials:

cycloaliphatic polyisocyanate H12MDI 4,4' -dicyclohexylmethane diisocyanate CAS number 79103-62-1 (Desmodur)^® W, Covestro Deutschland AG, Leverkusen, DE)

Carbodiimidization catalyst 3-methyl-1-phenyl-2-phosphole-1-oxide; CAS number 707-61-9 (Sigma-Aldrich Chemie GmbH, Munich, DE)

·Stabaxol^®P is an aromatic polycarbodiimide in powder form. Stabaxol^®P is used as a hydrolysis stabilizer for Thermoplastic Polyurethanes (TPU), Polyesters (PET), Polyamides (PA) and the like. Stabaxol^®P has a melting point of from 60 ℃ to 90 ℃. The carbodiimide content being at least 12.5% (company: Lanxess AG, kln, DE)

·Stabaxol^®P100 polycarbodiimide in powder form. Stabaxol^®P is used in particular as hydrolysis stabilizer for Polyesters (PET), Polyamides (PA) and the like. Stabaxol^®P100 has a melting point of 100 ℃ to 120 ℃. The carbodiimide content being at least 13% (company: Lanxess AG, K-inln, DE)

·BorchiGel^®LA thickener for polyacrylate-based aqueous coating systems (Borchers GmbH, Berghausener Str. 100, 40764 Langenfeld, DE)

·BorchiGel^®L75N liquid polyurethane-based thickeners (Borchers GmbH, Berghausener Str.100, 40764 Langenfeld, DE)

·Lucramul^®1820-liquid nonionic DispersionAgent base ethoxylated fatty alcohol (C16-C18) (LEVACO Chemicals GmbH, Chempark Leverkusen, 51368 Leverkusen, DE)

·Disperbyk^®VOC-free and solvent-free wetting and dispersing additives for aqueous paint systems and adhesives. Suitable for binder-free and binder-containing pigment concentrates. Specially optimized for emulsion systems (BYK-Chemie GmbH 46483 Wesel)

·BYK^® 024 VOC-free silicone-containing antifoam agents for aqueous dispersion paints, printing inks and overprint varnishes (Ü berdrucklack) and dispersion adhesives (BYK-Chemie GmbH 46483 Wesel)

·PUD 1: Dispercoll^®U2824 XP polyurethane dispersions based on polyester diols from Covestro Deutschland AG, 51365 Leverkusen; the solids content was about 40% by weight. The polymer contained approximately 18 mmol COOH groups per 100 g. The polymer has a glass transition temperature of about-40 ℃. The melting point of the crystalline segment in the polyurethane polymer chain is +47 ℃.

·PUD 2: Dispercoll^®U XP 2643 polyurethane dispersions based on polypropylene glycol from Covestro Deutschland AG, 51365 Leverkusen; the solids content was about 40% by weight. The polymer contained approximately 18 mmol COOH groups per 100 g. The polymer has a glass transition temperature of about-50 ℃.

The formula is as follows:

example 1 preparation of solid polycarbodiimide

524 grams of Desmodur were initially loaded in a 1L flat bottomed ground beaker^®W and reacted with 129 g of dibutylamine over 2 hours. Then 3.25 g of 3-methyl-1-phenyl-2-phospholene oxide was added and the carbodiimidization was started by heating the reaction mixture to 180 ℃. The reaction mixture was held at this temperature for 60 hours. The polycarbodiimide resin was then poured onto a metal plate, thereby curing it.

The polycarbodiimide resin has a glass transition temperature of +35 ℃.

The solid polycarbodiimide (example 1) was ground to a suitable particle size dv50 < 100 μm by grinding in a knife mill or jet mill (company: Hosowaka-Alpine, model 100 AFG).

Examples	dv10	dv50	dv90	Carbodiimide content [ meq DCC/g]
					1a	15.0	65.8	186	3.0
1b	6.3	20.8	50.9	3.0
					1c	1.1	3.4	7.7	3.3

Dv values in μm.

2a and 2b areComparative examples not according to the invention. These polycarbodiimide powders are used as a packageHydrolysis stabilizers for polymers containing polyester segments (polyesters, TPUs, etc.).

For better comparability, the carbodiimide content [ meq DCC/g ] was calculated from the values in the data sheet

。

Preparation of aqueous formulations containing polycarbodiimide powders:

examples 3a and 3b polycarbodiimide powders 1a or 1b, 100g of water, 10 g of Lucramul^®1820-liquid and 2.6 g BorchiGel^®ALA was added to the beaker and mixed with the dissolver disc at 3000 rpm for 5 minutes. A pseudoplastic paste is formed which can be stirred directly into the polymer dispersion.

Example 4 100g of polycarbodiimide 1c, 142 g of water, 20 g of Disperbyk^®191. 1.4 g BYK^®024 and 4 g BorchiGel^®L75N was added to the beaker and mixed with a dissolver disc at 3000 rpm for 5 minutes. A viscous paste is formed which can be stirred directly into the polymer dispersion.

Examples 5 and 6 100g polycarbodiimide examples 2a or 2b, 136 g water, 20 g Disperbyk^®191. 1.4 g BYK^®024 and 4 g BorchiGel^®L75N was added to the beaker and mixed with a dissolver disc at 3000 rpm for 5 minutes. A viscous paste is formed which can be stirred directly into the polymer dispersion.

Polycarbodiimide powder	Aqueous formulations of polycarbodiimide powders
		1a	Example 3a
1b	Example 3b
		1c	Example 4
2a	Example 5
		2b	Example 6

Reactive polymer dispersion:

all amounts are in g.

Comparative example using solid polycarbodiimide as hydrolysis stabilizer

All amounts are in g

The examples marked with x are comparative examples.

As a result:

oscillation measurement:

vibration measurements were performed on the dried adhesive film. For this purpose, dispersion examples 7,10, 11, 14, 18 and 19 were poured into teflon dishes so that the adhesive polymer had a layer thickness of approximately 1 mm after drying. After 1 week of storage at 23 ℃ and 50% relative humidity, the film samples were investigated in an oscillatory rheometer (ARES, TA-Instruments).

Softening temperature of adhesive joint:

The crosslinking of the solid polycarbodiimides (examples 2a and 2b and 3) in the adhesive layer, which is produced from the polyurethane dispersions PUD 1 and PUD 2, is well-defined. The softening temperature of the adhesive joint increases with increasing temperature and with increasing heat application time. The increase in softening temperature is directly attributable to polymer crosslinking and thus to a decrease in flowability of the adhesive polymer at elevated temperatures.

The adhesive coated substrates were stored for 1 month at 23 ℃/50% relative humidity:

the adhesive coated substrates were stored for 2 months at 23 ℃/50% relative humidity:

the stability of the reactive adhesive layer on the substrate is likewise clear. Adhesive joints can be produced even after 2 months storage of the coated substrates, wherein the softening temperature is higher than the softening temperature of the adhesive polymer without polycarbodiimide crosslinker (comparative examples 7 and 14).

Stability of polycarbodiimide powders in aqueous formulations:

Aqueous polycarbodiimide suspensions example 3 were stored at 23 ℃. After dissolving the dried polycarbodiimide resin in xylene, the carbodiimide concentrations of the fresh polycarbodiimide suspension and the polycarbodiimide suspension stored for 1 month or 2 months were determined.

Ageing of aqueous polycarbodiimide suspensions	Example 3
		Fresh and fresh	3.2
1 week	3.3
		1 month	3.1
2 months old	3.0

All values are in meq DCC/g polycarbodiimide powder.

The aqueous formulation of solid polycarbodiimide (example 3) is sufficiently stable for at least 2 months.

FIG. 1 shows that the crosslinking of the polymer chains of the dispersion polymer from PUD 1 by solid polycarbodiimide (example 3 b) is well defined:

i. the polymer from example 7 (without crosslinker) was G ' < G ' over the entire temperature range '

The polymer from example 10, G' increases above 94 ℃; g ' = G ' at 120 ℃ '

The polymer from example 11, G' increases above 86 ℃; g ' = G ' ' at 105 ℃.

FIG. 2 shows that the crosslinking of the polymer chains of the dispersion polymer from PUD 2 by solid polycarbodiimide (example 3 b) is well established:

i. the polymer from example 14 (without crosslinker) = G ' < G ' at 100 ℃ '

The polymer from example 18G ' > G ' ' over the entire temperature range. As the temperature increases, the distance between G ' and G ' ' increases

The polymer from example 19G ' > G ' ' over the entire temperature range. As the temperature increases, the distance between G' and G ″ increases.

FIG. 3 shows Staboxol as hydrolysis stabiliser^®P100 (example 2 a) has no crosslinking at up to 160 ℃. The value of G ' is lower than the value of G ' ' over the entire temperature range.

FIG. 4 shows Staboxol as hydrolysis stabiliser^®P (example 2 b) has no crosslinking at up to 160 ℃. The value of G ' is lower than the value of G ' ' over the entire temperature range.