WO2012136668A1

WO2012136668A1 - Coating material and method for coating extra-fine wires

Info

Publication number: WO2012136668A1
Application number: PCT/EP2012/056097
Authority: WO
Inventors: Michael Veith; Stefan Pfeifer; Torsten PIEPER
Original assignee: Fachhochschule Gelsenkirchen
Priority date: 2011-04-06
Filing date: 2012-04-03
Publication date: 2012-10-11
Also published as: DE102011001833A1; DE102011001833B4

Abstract

The present invention relates to an enamel for extra-fine copper wires, produced by the polymerization of suitable bis(alkoxyalkylsilylalkyl)imides or bis(alkoxyalkylsilylalkyl)amides.

Description

Coating material and method for coating ultra-fine wires

The present invention relates to the field of coatings for ultrafine wires, in particular copper fine wires.

Such ultrafine wires must be electrically insulated so that they can be used in electrical applications; This happens according to the current state of the art with organic paints. The special challenge is the guarantee of required material properties, such as a special thin layer thickness with a simultaneous high

Dielectric strength and high elasticity.

Increasing demands, in particular on the environmental compatibility of such paints have led to the constant search for new alternative paint systems for ultrafine wires.

It is therefore the task of finding a novel coating for fine wires, which in particular has an increased environmental impact.

This object is achieved by a very fine wire coating according to claim 1 of the present invention. Accordingly, there is proposed a microfine wire coating comprising polymerized bis (alkoxyalkylsilylalkyl) imides / bis (alkoxyalkylsilylalkyl) amides. It has been found that, surprisingly, such fine-wire coatings can be used and, in many applications, at least one of the following advantages can be observed:

- The synthesis of the coating can be carried out in aqueous or alcoholic solvents

- The synthesis can be carried out at room temperature, which is the

Energy efficiency significantly increased

- The coating itself can be carried out in alcoholic solvents or directly from water

The coating material is a hybrid material and not a block polymer with

inorganic / organic segments

- In the test tests carried out so far, multiple coatings were not recognizable as such, instead, a composite formed

- The coating has a high dielectric strength of 900-1200V (at a tested layer thickness of 4.3 - 6.9 μπι)

- The wires can be stretched up to 20%

- There is no outgassing of solvents or monomer residues

The term "superfine wire" includes, in particular, wires having an average diameter of 10-100 μm. Preferably, the ultrafine wires used predominantly consist of copper, so that this is a preferred embodiment of the present invention.

In a preferred embodiment, the bis (alkoxyalkylsilylalkyl) imide / bis (alkoxyalkylsilylalkyl) amides include silyl moieties having the structure:

(R ¹ ) _x (R ² ) _y -Si (CH ₂ ) _n - [R ³ - (CH ₂ ) _m ] _z - R ⁴ - with R ^{1 =} alkoxyl, preferably linear or branched C ₁ -C ₆ -alkoxy, more preferably ethoxy, methoxy, isopropyloxy, propyloxy

R ² = alkyl, preferably linear or branched C ₁ -C ₆ -alkyl, more preferably methyl, ethyl,

Propyl, isopropyl,

x = 1-3, y = 3-x

n = 1 to 5, preferably 2 or 3

z = 0 to 5, preferably 0, 1, or 2

R ³ = H or trimethylsilyl, where, in the case where z> 1, each R ^{3 of} each unit can be selected independently of one another,

m = 1 to 5, preferably 2 or 3, wherein in the case where z> 1, each m of each unit may be selected independently of each other,

R ⁴ = H, trimethylsilyl or carboxyl (in the case of imines)

The term "silyl unit" means a section or a partial structure of the preferred bis (alkoxyalkylsilylalkyl) imides according to the invention.

To (alkoxyalkylsilylalkyl) amides.

Particularly preferred are silyl units with R ^{1 =} ethoxy or methoxy, R ² = methyl or ethyl in combination with R ⁴ = H, n = 3 and z = 0.

Also preferred are silyl moieties with R ^{1 =} ethoxy, R ² = ethyl in combination with R ⁴ = H, n = 2 or 3 and z = 0.

Particularly preferred are silyl moieties with R ^{1 =} ethoxy or methoxy, R ² = methyl or ethyl in combination with R ³ = H, R ⁴ = H or carboxyl, n = 3, m = 2 and z = 1 or 2;

R ^{1 =} ethoxy, R ² = ethyl, z = 1 and R ⁴ = carboxyl are particularly preferred. It should be noted that according to a preferred embodiment of the invention, the very fine wire coating may also contain co-polymerized bis (alkoxyalkylsilylalkyl) imides / bis (alkoxyalkylsilylalkyl) amides comprising silyl units of the above structure but with x = 0 (ie without alkoxy groups), which may serve as "capping ends", which may be of interest depending on the specific application for obtaining smaller polymers.

In a preferred embodiment, the bis (alkoxyalkylsilylalkyl) imides include 5- or 6-membered cyclic imines and the bis (alkoxyalkylsilylalkyl) amides, respectively, their open-chain monoamides derived therefrom.

Particularly preferred are imines derived from the pyromellitic acid, i. Imines and amides of the following structure:

The bis (alkoxyalkylsilylalkyl) imides /

Bis (alkoxyalkylsilylalkyl) amides have the following structures:

(R ¹ ) x (R ² ) _y NR'lz-SiCR ¹ ) x (R ² ) _y

with R ^{1 =} alkoxyl, preferably linear or branched C ₁ -C ₆ -alkoxy, more preferably ethoxy, methoxy, isopropyloxy, propyloxy

Propyl, isopropyl,

x = 1-3, y = 3-x

n = 1 to 5, preferably 2 or 3

z = 0 to 5, preferably 0, 1, or 2

R ³ = H or trimethylsilyl, where, in the case where z> 1, each R ^{3 of} each unit can be selected independently of one another, m = 1 to 5, preferably 2 or 3, wherein in the case where z> 1, each m of each unit may be selected independently of each other,

R ⁴ = H or trimethylsilyl

Particularly preferred is R ^{1 =} ethoxy or methoxy, R ² = methyl or ethyl in combination with R ⁴ = H, n = 3 and z = 0.

Also preferred is R ^{1 =} ethoxy, R ² = ethyl in combination with R ⁴ = H, n = 2 or 3 and z = 0.

Particularly preferred is R ^{1 =} ethoxy or methoxy, R ² = methyl or ethyl in combination with R ³ = H, R ⁴ = H or carboxyl, n = 3, m = 2 and z = 1 or 2; even more preferred is R ^{1 =} ethoxy, R ² = ethyl, z = 1 and R ⁴ = carboxyl.

According to a preferred embodiment of the invention, the

Finest Wire Coating Polymerized Tetraalkoxysilanes / Trialkoxyalkylsilanes /

Dialkoxyalkylsilane.

The proportion (in parts by weight) of tetraalkoxysilanes / trialkoxyalkylsilanes / dialkoxyalkylsilanes based on the bis (alkoxyalkylsilylalkyl) imides /

Bis (alkoxyalkylsilylalkyl) amides of> 5% to <90% (in each case based on the starting materials before the polymerization), more preferably> 10% to <80% and most preferably from> 20% to <70%.

The term "tetraalkoxysilane / trialkoxyalkylsilanes / dialkoxyalkylsilanes" is understood to mean, in particular, that one of these components is present, but also two or all three.A particular preference is given to a mixture of trialkoxyalkylsilanes and

Dialkoxyalkylsilanen and a mixture of all three components. Preferred tetraalkoxysilanes are in particular tetraethoxysilane and tetramethoxysilane, more preferably tetraethoxysilane.

Preferred trialkoxyalkylsilanes are in particular triethoxyethylsilane,

Triethoxymethylsilane, trimethoxyethylsilane and trimethoxymethylsilane, more preferably triethoxymethylsilane.

Preferred dialkoxydialkylsilanes are in particular diethoxydiethylsilane,

Diethoxydimethylsilane, dimethoxydiethylsilane and dimethoxydimethylsilane, more preferably diethoxydimethylsilane.

Particular preference is given to mixtures comprising (in each case% by weight, based on the total weight of tetraalkoxysilanes / trialkoxyalkylsilanes / dialkoxyalkylsilanes) containing> 0% to <50% tetraalkoxysilane,> 1% to <90% trialkoxyalkylsilanes and> 10% to <100% Dialkoxyalkylsilane (where the sum of the wt% shares of course always gives 100%).

The invention also relates to a process for the preparation of a

Finest wire coating according to the invention, comprising the steps:

(a) Preparation of a suitable carboxyl compound, preferably a bisanhydride

(b) adding bis (alkoxyalkylsilylalkyl) amine for the preparation of

imides to (alkoxyalkylsilylalkyl) / amides to (alkoxyalkylsilylalkyl)

(c) Polymerization of bis (alkoxyalkylsilylalkyl) imides / bis (alkoxyalkylsilylalkyl) amides (d) optionally adding tetraalkoxysilane / trialkoxyalkylsilane / dialkoxyalkylsilane and subsequent hydrolysis

(e) applying the polymer to very fine wire

This has proven to be a suitable method for producing the very fine wire coating.

In step (a), bisanhydrides, e.g. Pyromellitic anhydride used. This is for the reason that by-products can be avoided. However, other suitable carboxylic compounds such as esters, halides, etc. may also be used.

According to a preferred embodiment, step (a) and / or (b) are carried out in alcohol or a water-alcohol mixture. It should (to avoid

Side reactions) the water content at max. 20 vol.% Lie. As alcohols primary alcohols are preferred, in particular ethanol and propanol.

According to a preferred embodiment, step (c) is carried out in water, alcohol or a water-alcohol mixture. As alcohols primary alcohols are preferred, in particular ethanol and propanol.

According to a preferred embodiment, step (d) is carried out so that initially the tetraalkoxysilanes / Trialkoxyalkylsilane / Dialkoxyalkylsilane be submitted and then carried out a hydrolysis so that water in such a large molar amount based on the proportion of ethoxy groups in the

Tetraalkoxysilanes / Trialkoxyalkylsilanen / Dialkoxyalkylsilanen is added that a theoretical hydrolysis> 10 to <100%, preferably> 20 to <80% results. Preference is then allowed to stand for 20-28 h, preferably 24 h.

According to an alternative embodiment of the invention, step (d) is performed prior to steps (a) through (c), i. First, the tetraalkoxysilanes / Trialkoxyalkylsilane / Dialkoxyalkylsilane be submitted and (preferably as stated above) hydrolyzed, then the representation of the polymer takes place from the

To (alkoxyalkylsilylalkyl) imides / amides to (alkoxyalkylsilylalkyl).

According to a still alternative embodiment of the invention, steps (a) to (c) on the one hand and step (d) on the other hand take place in parallel, i. only the two polymers are combined before step (e). In this case, it is particularly preferred that after the (preferably as stated above) hydrolysis of the tetraalkoxysilanes / Trialkoxyalkylsilane / dialkoxyalkylsilanes the pH is adjusted to> 1 to <5 and then allowed to stand for 20-28 h, preferably 24 h and then neutralized (if necessary with cooling). Only then does the combination with the polymerized bis (alkoxyalkylsilylalkyl) imides / bis (alkoxyalkylsilylalkyl) amides take place.

According to a preferred embodiment, step (e) is carried out in water, alcohol or a water-alcohol mixture. As alcohols primary alcohols are preferred, in particular ethanol and propanol.

The present invention also relates to a use of a

Feinstdrahtbeschichtung invention for

microelectronic components

insulators

electrical ladder

- capacitors Do the washing up

conductor tracks

Inductive components

transformers

transistors

generators

the above uses in particular for the following areas:

acoustics

Medical

Automotive engineering

- Home appliances

- Aerospace

- Entertainment technology

Surprisingly, it has been found in further investigations that the

coating according to the invention is also suitable for other applications; this represents an independent inventive achievement.

Thus, the present invention relates to a coating for separators of accumulators and / or batteries, in particular Li-ion accumulators and / or batteries, comprising polymerized bis (alkoxyalkylsilylalkyl) imides /

To (alkoxyalkylsilylalkyl) amides. These can be further specified as mentioned above.

It has been found that such coatings often have advantageous properties, especially the tendency to form so-called "pinholes" is often reduced, sometimes to the extent that virtually no pinholes occur in the coating. The following is the preparation and other properties of the coating for

Separators further explained and described:

Through targeted hydrolysis, the coating can be prepared in particle or gel form; this is preferred depending on the application. The porosity of the material is u.a. determined by the amount of water to the amount of alkoxide groups present, which is used for the hydrolysis.

The coating is preferably applied to the electrodes by dip coating, spray coating or spin coating. The coating preferably has a thickness of> 1 μπι to <10 cm.

Preferably, after application, the product is dried, preferably at a temperature of> 20 ° C to <275 ° C. The dried product then has no subsequent syneresis in many applications, which could lead to cracks in the layer.

According to a further embodiment of the invention, in particular for the further adjustment of the porosity, particles of another material with a diameter between> 10- <500 nm are integrated into the raw material. These are preferably made

Silica. If the electrode material is treated with Si precursors prior to coating, it is often possible to achieve an improvement in the adhesion between separator and electrode.

Furthermore, the present invention relates to a coating for organic electronic components comprising polymerized bis (alkoxyalkylsilylalkyl) imides /

To (alkoxyalkylsilylalkyl) amides. These can be further specified as mentioned above. The term "organic electronic components" are organic transistors, organic light-emitting diodes, light-emitting electrochemical cells, organic solar cells, photodiodes and organic photovoltaic generally understood.

Furthermore, the present invention relates to an insulating film comprising

polymerized bis (alkoxyalkylsilylalkyl) imides / bis (alkoxyalkylsilylalkyl) amides. These can be further specified as mentioned above.

The above-mentioned and the claimed components to be used according to the invention described in the exemplary embodiments are not subject to special conditions of size, shape, material selection and technical design, so that the selection criteria known in the field of application can be used without restriction.

Further details, features and advantages of the subject matter of the invention will become apparent from the subclaims and from the following figures and the description of an example of a Feinstdrahtbeschichtung, which is to be understood purely illustrative.

1 shows a SEM photograph of a fine wire with a coating according to an embodiment of the present invention

FIG. 2 shows a SEM photograph of a fine wire with a coating according to an embodiment of the present invention in the wound state. FIG.

Example I

In a 250 ml two-necked flask, 0.05 mol of pyromellitic anhydride are added.

Subsequently, so much ethanol is added to the anhydride that a solution of 20 percent by mass is formed. Finally, 0.1 mol of aminopropyltriethoxysilane becomes the heterogeneous Solutions dripped quickly. The solution is stirred until a clear solution is obtained.

The resulting coating solution can be used after about 24 hours. Coating tests:

The coating experiments were carried out on a Aumann 110 baked-on coating unit. The paint is applied over a fleece. The fleece is supplied with paint during the coating experiment via a discontinuous pump. The wire (copper wire with a thickness of 20μιη) is passed through the web at a speed of 300m / min and then cured at a constant speed in an oven at 370 ° C. The coating process is repeated a total of 12 times.

Analysis of coating properties:

The enamelled wire was tested on an analysis line built by MAG and Isodra for pinholes, tensile strength and breakdown voltage.

In addition, the surfaces of the coated wires with a SEM

(Scanning Electron Microscope) in unwk disgusted (Fig. 1) and wound state (Fig. 2) optically mapped. The resolution is five times higher in FIG. 1 than in FIG. 2

The coated wires did not show pinholes. The breakdown voltage was

an average of about 900 V. With the scanning electron microscope it was shown that the individual paint jobs form a single layer, ie network with each other. Furthermore No holes could be found both in the wound and in the unwound state.

The individual combinations of the components and the features of the already mentioned embodiments are exemplary; the exchange and substitution of these teachings with other teachings contained in this document with the references cited are also expressly contemplated. The person skilled in the art recognizes that variations,

Modifications and other embodiments described herein may also occur without departing from the spirit and scope of the invention. Accordingly, the above description is illustrative and not restrictive. The word used in the claims does not exclude other ingredients or steps. The unanimous article "a" does not exclude the meaning of a plural The mere fact that certain measures are recited in mutually different claims does not make it clear that a combination of these measures can not be used to advantage as defined in the following claims and the associated equivalents.

Claims

1. Superfine wire coating comprising polymerized

To (alkoxyalkylsilylalkyl) imide / bis (alkoxyalkylsilylalkyl) amides

2. Very fine wire coating according to claim 1, wherein the

Bis (alkoxyalkylsilylalkyl) imide / bis (alkoxyalkylsilylalkyl) amide silyl units having the structure:

(R ¹ ) _x (R ² ) _y -Si- (CH ₂ ) _n - [NR ³ - (CH ₂ ) _m ] _z -NR ⁴ -Carboxyl with R ^{1 =} alkoxyl, preferably linear or branched Ci-C ₆ alkoxyl , still preferably ethoxy, methoxy, isopropyloxy, propyloxy

R ² = alkyl, preferably linear or branched C ₁ -C ₆ -alkyl, more preferably methyl,

Ethyl, propyl, isopropyl,

x = 1-3, y = 3-x

n = 1 to 5, preferably 2 or 3

R ³ = H or trimethylsilyl

z = 0 to 5

m = 1 to 5, preferably 2 or 3, wherein in the case where z> \, each m of each unit can be selected independently of each other,

R ⁴ = H or trimethylsilyl

3. Very fine wire coating according to claim 1 or 2, wherein the

Bis (alkoxyalkylsilylalkyl) imides 5- or 6-membered cyclic imines and the bis (alkoxyalkylsilylalkyl) amides include their open-chain monoamides derived therefrom.

4. Superfine wire coating according to any one of claims 1 to 3, wherein the bis (alkoxyalkylsilylalkyl) imide / bis (alkoxyalkylsilylalkyl) amides

Pyromellithsäi diimides or their (partially) open-chain monoamides included.

5. A method for producing a Feinstdrahtbeschichtung according to any one of claims 1 to 4, comprising the steps

(a) Preparation of a suitable carboxyl compound, preferably a bisanhydride

(b) adding bis (alkoxyalkylsilylalkyl) amine for the preparation of

imides to (alkoxyalkylsilylalkyl) / amides to (alkoxyalkylsilylalkyl)

(c) Polymerization of

To (alkoxyalkylsilylalkyl) imides / bis (alkoxyalkylsilylalkyl) amides

(d) optionally adding tetraalkoxysilane / trialkoxyalkylsilane /

Dialkoxyalkylsilane and subsequent hydrolysis

(e) applying the polymer to very fine wire

6. The method according to claim 5, wherein step (a) and / or (b) are carried out in alcohol or a water-alcohol mixture

7. The method according to claim 5 or 6, wherein step (a) and / or (b) at a

Temperature from 0 ° C to 50 ° C, preferably at room temperature

8. The method according to any one of claims 5 to 7 wherein step (c) is carried out water, alcohol or a water-alcohol mixture.

9. The method according to any one of claims 5 to 8, wherein step (e) is carried out in water, alcohol or a water-alcohol mixture.

10. Use of a very fine wire coating according to one of claims 1 to 4 or produced by the method according to one of claims 5 to 9 for microelectronic components

insulators

electrical ladder

- capacitors

Do the washing up

conductor tracks

Inductive components

transformers

transistors

generators