2,4,7,9-Tetramethyl-5-decyne-4,7-diol-based solvent-free composition

Abstract

To provide a composition as a wetting agent and / or defoamer, which is essentially free from volatile organic compounds compared to comparable compositions and which is storage-stable.SOLUTION: A solvent-free composition contains 2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethoxylates thereof, and polyethylene glycols, where the composition contains water and where the concentration of 2,4,7,9-tetramethyl-5-decyne-4,7-diol is greater than 40 wt.% based on the weight of the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to 2,4,7,9-tetramethyl-5-decyne-4,7-diol based solventless compositions for reducing the surface tension of aqueous, solvent-containing systems, their use, and their preparation. [Background technology]

[0002] The ability to reduce surface tension is very important in the application of water-based formulations, since the reduction in surface tension affects the improvement of the wetting of the substrate. Examples of water-based compositions include coatings, inks, wetting agents, cleaning compositions, and agricultural formulations. The reduction of surface tension in water-based systems is generally achieved by adding surfactants, which results in improved surface wetting, fewer defects, and better leveling. When the system is at rest, it is important to reduce the static surface tension. The dynamic surface tension provides a measure of the ability of surfactants to orient on the newly created surface.

[0003] Acetylenic glycol-based surfactant additives, such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, are known for their excellent static and dynamic surface tension reduction capabilities, and have few of the negative characteristics of traditional nonionic and anionic surfactant additives.

[0004] The additive 2,4,7,9-tetramethyl-5-decyne-4,7-diol is a waxy solid with low water solubility and volatility, available for example under the trade name SURFYNOL® 104 (Evonik). Therefore, before the additive can be used, for example as a wetting agent, it must be melted and / or further dissolved in an organic solvent at the preferred use concentration of about 50%. These additional steps mean more effort and costs for users in the coatings industry.

[0005] To avoid these additional steps, 2,4,7,9-tetramethyl-5-decyne-4,7-diol is already available on the market in a suitable organic solvent (e.g., 2-ethylhexanol, 2-butoxyethanol, dipropylene glycol monomethyl ether, ethylene glycol, propylene glycol, or 2-propanol) at a desired solution concentration of 50% or 75%. Known trade names include Surfynol® 104A or SURFYNOL® 104E.

[0006] Significant limitations are expected in the future for the use of organic solvents in coating compositions or formulations. These are due, inter alia, to various national and international guidelines (European Decopaint Guideline 2004 / 42 / CE) for limiting VOC (volatile organic compounds) emissions from coating materials and reducing the health risks to processors and users from volatile and semi-volatile compounds (VOCs and SVOCs) (see German Building Standard (AgBB), or German Sustainable Building (DGNB), or Leadership in Built Environment (LEED)).

[0007] Patent Document 1 discloses a comparative test of a water-soluble wetting agent composition containing 2,4,7,9-tetramethyl-5-decyne-4,7-diol and an alcohol alkoxylate, or ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol and an alcohol alkoxylate, and ethylene glycol (Table 1), but does not provide any information regarding storage stability. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent Publication No. 7,018,963 Summary of the Invention [Problem to be solved by the invention]

[0009] It is therefore an object of the present invention to provide a composition as a wetting agent and / or defoamer which is essentially free of volatile organic compounds and is storage stable compared to similar compositions. [Means for solving the problem]

[0010] Therefore, to achieve this goal, the following ingredients are required: - 2,4,7,9-tetramethyl-5-decyne-4,7-diol, - its ethoxylates, and - Polyethylene glycol A solvent-free composition comprising: the composition comprises water, A solvent-free composition is proposed, characterized in that the concentration of the 2,4,7,9-tetramethyl-5-decyne-4,7-diol exceeds 40% by weight of the composition.

[0011] In the context of this specification, solvent-free means that no solvents containing volatile organic compounds are used that comply with the requirements of the European Decopaint guideline 2004 / 42 / CE.

[0012] The composition according to the invention preferably does not contain organic solvents such as 2-ethylhexanol, 2-butoxyethanol, dipropylene glycol monomethyl ether, ethylene glycol, propylene glycol or 2-propanol.

[0013] It was therefore surprising that 2,4,7,9-tetramethyl-5-decyne-4,7-diol could be dissolved in water in such a way that the use of organic solvents could be dispensed with.

[0014] Quite unexpectedly, the compositions according to the invention do not show phase separation in storage stability tests, even under extreme temperature fluctuations after thawing.

[0015] Any crystals formed during the storage stability test can be easily reincorporated (ie, can be reincorporated without high shear forces and / or heat).

[0016] The composition according to the invention preferably has a concentration of 2,4,7,9-tetramethyl-5-decyne-4,7-diol of not more than 80% by weight, preferably not more than 70% by weight, particularly preferably not more than 60% by weight, based on the weight of said composition.

[0017] It was also completely unexpected that the concentration of this 2,4,7,9-tetramethyl-5-decyne-4,7-diol could be adjusted. Users can use the solvent-free composition according to the present invention without modifying the formulation.

[0018] The polyethylene glycol preferably has a molar mass of 200 g / mol to 1,000 g / mol, preferably 300 g / mol to 800 g / mol, particularly preferably 400 g / mol to 600 g / mol.

[0019] The composition according to the present invention preferably contains an ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 1 to 10 moles, preferably 3 to 10 moles, of ethylene oxide, which are known, for example, under the trade names SURFYNOL® 465, SURFYNOL® 440, or SURFYNOL® 420 (manufactured by Evonik).

[0020] The ethoxylated derivatives or ethoxylates of 2,4,7,9-tetramethyl-5-decyne-4,7-diol are used synonymously.

[0021] According to a preferred embodiment of the composition according to the invention, said composition comprises: 40% to 80% by weight, preferably 41% to 70% by weight, particularly preferably 42% to 60% by weight, of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, - 0.5% to 15% by weight, preferably 1.0% to 10.0% by weight, particularly preferably 2.0% to 8.0% by weight of 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate, from 35% to 55% by weight, preferably from 38% to 50% by weight and particularly preferably from 40% to 45% by weight of polyethylene glycol, and 1.0% to 15% by weight, preferably 2.0% to 12.0% by weight, particularly preferably 3.0% to 10.0% by weight of water Including, The amounts of each component mentioned above total 100% by weight and are amounts relative to the composition.

[0022] The present invention further preferably relates to the use of the composition according to the invention as a wetting agent, defoamer or dispersing aid in a coating composition.

[0023] The coating composition can be used in the fields of lacquers, paints and inks.

[0024] The compositions according to the invention are preferably used for the formulation of auxiliaries in the fields of agriculture, building materials, plant protection, textile finishing, hydrophobization and electroplating, latex dipping, metalworking fluids and printed circuit board coatings.

[0025] The present invention also relates to a method for producing a method for manufacturing a semiconductor device comprising the steps of: a. providing polyethylene glycol; b. adding water; c. adding an ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; and d. adding molten 2,4,7,9-tetramethyl-5-decyne-4,7-diol The present invention also relates to a method for producing the composition.

[0026] By following these steps, it has been possible to establish that 2,4,7,9-tetramethyl-5-decyne-4,7-diol can be better incorporated without fear of its concentration being reduced in the composition according to the invention, for example by its adhesion to the container. The reduction of 2,4,7,9-tetramethyl-5-decyne-4,7-diol in the industrial production of the composition according to the invention is much more serious than in the laboratory scale.

[0027] The composition according to the invention therefore offers many advantages: it is storage stable and can be easily incorporated into aqueous formulations and water, the systems made from it have low surface tension and low foaming behavior.

[0028] By being free of solvents containing volatile organic compounds, the compositions according to the present invention refer to reduced-VOC and / or near-VOC-free compositions.

[0029] The following examples are presented merely to illustrate the invention to one of ordinary skill in the art and are not intended to limit the claimed subject matter or methods in any way. EXAMPLES

[0030] Equipment - Binder circulating air oven -VMA Getzmann melter / gear disc, CA20M1 model

[0031] 1. Preparation of the Composition First, SURFYNOL® 104 (Evonik) was melted in a circulating air oven at 60°C. PEG 400 (Dow) was first placed in a 180 mL plastic beaker. Water was slowly added while stirring at 500 revolutions per minute (rpm), stirred with a gear disc (φ4 cm) and stirred for an additional 5 minutes. Then, SURFYNOL® 440 (Evonik) was added while stirring, and finally, pre-melted SURFYNOL® 104 was added. The composition was then stirred at 500 rpm for an additional 15 minutes. The weight percentages of the ingredients are set forth in Table 1.

[0032] 2.Storage stability experiment Various experiments were carried out to test the storage stability of the compositions according to the invention, and for this purpose, various conditions which may be effective for the storage of the compositions were simulated. 2a) Room temperature The prepared compositions were visually evaluated after one day and one week of storage at room temperature, and the visual results are shown in Table 1. - The compositions Z1 and Z2 according to the invention were clear and liquid after 1 day and after 1 week. The comparative compositions VZ1 and VZ2 show a low solubility of SURFYNOL® 104 in water, which is known from the prior art. - Comparative compositions VZ3 to VZ6 show that SURFYNOL® 104 is insoluble in PEG 400 at concentrations above 40% by weight. - Comparative compositions VZ7 and VZ8 could be converted to a liquid state with the use of water, although VZ8 showed phase separation and became partially solid after one week. VZ7 appeared to be storage stable without the addition of SURFYNOL® 440, but this was disproved by further experiments (see below). 2b) Store at -5℃ for 1-4 days, then thaw for 5 hours The prepared compositions were stored at -5°C and in each case visually evaluated after 1 day, then thawed for 5 hours after 4 days and finally evaluated. The results are shown in Table 2. In this experiment, only VZ1, VZ2, VZ7 and Z1, Z2 were selected because they were deemed suitable under "mild" conditions as explained in 2a). The other comparative compositions were not considered because they were not storage stable. It was shown that VZ7 was not stable at temperatures of -5°C for short periods (4 days). Compositions Z1 and Z2 of the invention as well as VZ1 were stable under these conditions. 2c) Extreme conditions The prepared compositions were stored at -20°C for 4 days in a 16 hour cycle, then thawed at room temperature (RT) for 8 hours. After each step, they were visually inspected. The results are shown in Table 3. In this experiment, the same composition as in 2b) was chosen. The compositions Z1 and Z2 of the present invention have been demonstrated to be stable even under these extreme conditions. In the case of VZ1, the user had to thaw the composition. In the case of the compositions of the present invention, there is no need to wait for thawing. Thus, the user can save time and costs. [Table 1] [Table 2] [Table 3]

Claims

1. - 40% to 80% by weight of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; - 0.5% to 15% by weight of the ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, from 35% to 55% by weight of polyethylene glycol, and - 1.0% to 15% by weight of water A composition comprising: The amounts of the components total 100% by weight and are expressed relative to the composition.

2. 2. The composition according to claim 1, wherein the concentration of said 2,4,7,9-tetramethyl-5-decyne-4,7-diol is 41 to 70% by weight based on the weight of said composition.

3. 3. The composition according to claim 1, wherein the molar mass of said polyethylene glycol is between 200 g / mol and 1,000 g / mol.

4. The composition according to any one of claims 1 to 3, characterized in that the ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol contains from 1 mole to 10 moles of ethylene oxide.

5. Use of the composition according to any one of claims 1 to 4 as a wetting agent, defoamer or dispersing aid in a coating composition.

6. Use of the composition according to any one of claims 1 to 4 in the formulation of lacquers, paints, inks and auxiliaries in the fields of agriculture, building materials, plant protection, textile finishing, hydrophobization and electroplating, latex dipping, metal working fluids and printed circuit board coatings.

7. The following steps: a. providing polyethylene glycol; b. adding water; c. adding an ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; and A method for making the composition of any one of claims 1 to 4, comprising the step of: adding molten 2,4,7,9-tetramethyl-5-decyne-4,7-diol.

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