CA2061325A1 - Amphiphilic polymers containing silane units and film comprising at least one monomolecular layer produced therefrom - Google Patents
Amphiphilic polymers containing silane units and film comprising at least one monomolecular layer produced therefromInfo
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- CA2061325A1 CA2061325A1 CA002061325A CA2061325A CA2061325A1 CA 2061325 A1 CA2061325 A1 CA 2061325A1 CA 002061325 A CA002061325 A CA 002061325A CA 2061325 A CA2061325 A CA 2061325A CA 2061325 A1 CA2061325 A1 CA 2061325A1
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- weight
- structural units
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
Abstract of the disclosure:
Amphiphilic polymers containing silane units and film comprising at least one monomolecular layer produced therefrom Amphiphilic copolymers containing silanyl groups and composed of derivatives of acrylic and/or methacrylic acid are described, which copolymers are suitable for the production of layer elements by the Langmuir-Blodgett method. Layer elements of this type can be used for optical waveguide systems and for the production of optical filters and for lithographic purposes.
Amphiphilic polymers containing silane units and film comprising at least one monomolecular layer produced therefrom Amphiphilic copolymers containing silanyl groups and composed of derivatives of acrylic and/or methacrylic acid are described, which copolymers are suitable for the production of layer elements by the Langmuir-Blodgett method. Layer elements of this type can be used for optical waveguide systems and for the production of optical filters and for lithographic purposes.
Description
2~32~
HOECHST AKTIENGESELLSCHAFT HOE 91/F 075 Dr. SP/rh Description Amphiphilic polymers containin~ silane units and film comprising at least one monomolecular layer produced therefrom The invention relates to specific amphiphilic copolymers containing silane units, a film comprising at least one monomolecular layer of these molecules on a solid support (= so-called layer elements), and a process for the preparation of the layer elements and their use.
Ordered layers of organic polymers having long-chain side groups are predominantly prepared by using the Langmuir-Blodgett (LB) method. In this method, molecules are spread on a water surface and the long alkyl side groups are aligned in parallel by decreasin~ the area per molecule. At a constant pressure, the molecules are applied to a substrate by immersion and withdrawal. Per dipping operation, one monomolecular layer is transferred with retention of its order.
LB films are constructed by using amphiphilic molecules, i.e. molecules having a hydrophilic end (a "head") and a hydrophobic end (a "tail"). In order to achieve higher stability of the LB films, polymeric LB films have also already been prepared.
Preparation of polymeric LB films can be carried out by polymerization of unsaturated amphiphiles after formation of the monomer film. However, organic polymers having long alkyl side chains have also already been used directly for preparation of the layer (WO 83J03165, R. Elbert, A. Laschewsky and H. Ringsdorf, J. Am. Chem.
Soc. 107, 4134-4141 (1985)). Copolymer films have also already been described (A. Laschewsky, H. Ringsdorf, G. Schmidt and J. Schneider, J. ~m. Chem. Soc. 109, 788-796 (1987)). In these copolymers, one of the comonomers carries at least one long alkyl chain, while .: . ~ : :
: , 2~325 -the second monomer is water-soluble, or carries at least - polar and hydrophilic groups. If such polymer films are intended to be used as resist materials, such as, for example, described by R. Jones, C.S. Winter, R.H. Tredgold, P. Hodge and A. Hoorfar, Polymer 28, 1619-1626 (1987), the problem of insufficient etching stability of these films during plasma etching arises.
However, it is known from resist technology that the etching stability of photoresists in an oxygen plasma can be drastically increased by incorporating silicon com-pounds. Thus, aliphatic and~or aromatic hydroxyl-carrying polymeric binders have been described which contain silanyl groups in the side chain which, as components of a photosensitive mixture, give this mixture increased resistance to plasma etching ~EP-A-0,337,188). The photosensitive layer, which is formed by spin-coating the substrate with a resist solution containing such a binder and compounds from the class of compounds of o-quinone diazides, has a layer thickness of 0.3 to 10 ~m. A
disadvantage for microelectronic applications, for example high-resolution electron beam lithography, is the relatively high layer thickness of resist films of this type.
Furthermore, Langmuir-Blodgett layers of amphiphilic polysiloxanes are known (Adv. Mater. 3 (1991), 27). It is true that they have good etching resistance in an oxygsn plasma, but for many applications they have only insuffi-cient temperature resistance, owing to the siloxane main chain.
Accordingly, the object is to prepare polymers from which Langmuir-Blodgett films can be formed which have improved resistance to temperature and plasma etching.
The in~ention relates to amphiphilic copolymers contain-ing silanyl groups and structural units derived from at least one monomer of the formula I
: -2~ 32~
~ _ 3 -O Y
A-Bn-tCH~m-X-~-c- CH2 (I) and at least one monomer of the formula II
OY
D-E-L-C-C - CH2 ( I I ) in which A- is CH3- or CF3-, -B- is -CH2- or -CF2-, n is an integer from 5 to 25, m is an integer from ~ero to 12, -X- is -O-, -NR1- or -Z-, in which R~- is H-, CH3-(CH2)n- or CF3-(CF2)n-(CH2)~--Z- is -X'-(CH2)p-X' or O O
. ~
-X'-C-(CH2),-C-X'-(CH2)p-X', p is an integer from 2 to 10, l is an integer from 1 to 10 and -X'- is -O- or -NR~
-Y is -H, -CH3, -CN, -Cl, -Br or -F, -D is -SiR2(SiR23)2, Si(SiR23)3, -SiR22-SiR23 or -(SiR22)2-SiR23, in which R2 is C,-C3-alkyl, -E- is Cl-C4-alkylene and O
-L- is -o-~-NRl-~-NH-c-x~-(cH2)p-xl- or -NH-C-(O-CH2-C:~2)p-O- ist.
Preferred structural units derived from monomers of the formula I carry only one long side chain, i.e. the function group -~-, which is:-O-, -NH- or -Z- and -X'-g which is -O- or -NH-.
', :
" 2~6~32~
Preferred structural units deri~ed from monomers of the formula II are those in which -D is -(SiR2~-SiRZ3 and R2 is C'1-C3-alkyl, in particular methyl, -E- is C2-alkylene, p -L- is -NH- or -NH-C-O-cH2-cH2-O- and -Y is -H or -CH3.
The synthesis of the monomers of the formula I can be carried out by known methods ~y reaction of a vinylcar-boxylic acid or an activated derivative of this car-boxylic acid, for example an acid halide, with a long-chain alcohol or amine of the formula IV
A - Bn - (CH2)~ - X' - H (IV) in which A-, -B-, -X'-, m and n have the abovementioned meaning.
Monomers o~ the formula I containing structural units Z
can be prepared first by reaction of a dicarboxylic acid of the formula (V) HOOC - (CH2)l - COOH (V~
or of an activated derivative of this dicarboxylic acid, such as, for example, of an acid anhydride, an ester or an acid halide, with an unsaturated alcohol or amine of the formul~ (VI) Y O
- CH2 = C - C - X' - (CH~)p - X' - H (VI) in which 1, p, Y and X' have the abovementioned meaning, to give the monoester, followed by condensation with a long-chain alcohol or amine of the formula VII
- . . :.
.
2~6132~
A - Bn - (CH2)m - X' H (VII) in which A, B, X', n and m have the abovementioned meaning.
However, they can also be prepared by the reverse reac-tion sequence, i.e. by reaction of the dicarboxylic acid of the formula (V) or of one of its reackive derivatives with a long-chain alcohol or am:ine of the formula (VII), followed by esterification of the intermediate with the unsaturated alcohol of the formula (VI).
The monomers containing silanyl groups of the formula II
can be prepared by reaction of a vinylcarboxylic acid or of an activated derivative thereof with a silylating reagent of the formula VIII
D - E - L' - H (VIII) in which -L'- is -NR1 or -O-, and Rl, D and L have the abovementioned meaning.
Silylating reagents of the formula VIII are described in EP-A-0,336,276.
The monomers of the formula II can furthermore be syn-thesized by reaction of isocyanato-containing silylating reagents of the formula IX
D - E - N = C = O (IX) in which D and E have the abovementioned meaning, with an unsaturated alcohol or amine of the formula VI or of the formula X
.
. .: -- . : . . . : . ~ : .
2~3~5 CH2 = C-C- O-(~H2-CH2-O)p~H (X) Y O
Copolymers (i.e. ter- and multipolymers) which in addi-tion to the structural units derived from monomers of formula I and II contain at least one structural unit derived from further functional comonomers, for example those leading to radiation-induced crosslinking of the polymers, are also suitable ~or the purposes of the invention. Further comonomers are also monomers having long alkyl chains, for example monomers such as described by Jones et al., Elbert et al. and Laschewsky et al. in the abovementioned publication~ and in WO 83/03165.
Moreover, hydrophilic, preferably water-soluble, vinyl monomers, such as, for example, itaconic acid, fumaric acid, maleic acid, acrylic acid, cyanoacrylic acid and methacrylic acid or derivatives thereof are suitable as comonomers.
Particular preference is given to those comonomers carry-ing radiation-crosslinkable units.
The proportion of structural units derived from silanyl-containing monomers of the formula II in the copolymercan be 5 to 98, preferably 30 to 85 and in particular 30 to 70, mol ~. The proportion of structural units derived from monomers of the formula I in the copolymer can be 95 to 2, preferably 70 to 15 and in particular 70 to 30, mol %, the proportions of the structural units adding up to a total of lO0 mol %.
In copolymers containing structural units derived from at least one mon~mer each of the formula I and II and at least one further functional comonomer, preferably containing a radiation-crosslinkable unit, the propor~ion of structural units derived from monomers of the formula I can be 90 to 5, preferably 60 to 20, mol %, the proportion of structural units derived from monomers of - ~ , , ::
:
HOECHST AKTIENGESELLSCHAFT HOE 91/F 075 Dr. SP/rh Description Amphiphilic polymers containin~ silane units and film comprising at least one monomolecular layer produced therefrom The invention relates to specific amphiphilic copolymers containing silane units, a film comprising at least one monomolecular layer of these molecules on a solid support (= so-called layer elements), and a process for the preparation of the layer elements and their use.
Ordered layers of organic polymers having long-chain side groups are predominantly prepared by using the Langmuir-Blodgett (LB) method. In this method, molecules are spread on a water surface and the long alkyl side groups are aligned in parallel by decreasin~ the area per molecule. At a constant pressure, the molecules are applied to a substrate by immersion and withdrawal. Per dipping operation, one monomolecular layer is transferred with retention of its order.
LB films are constructed by using amphiphilic molecules, i.e. molecules having a hydrophilic end (a "head") and a hydrophobic end (a "tail"). In order to achieve higher stability of the LB films, polymeric LB films have also already been prepared.
Preparation of polymeric LB films can be carried out by polymerization of unsaturated amphiphiles after formation of the monomer film. However, organic polymers having long alkyl side chains have also already been used directly for preparation of the layer (WO 83J03165, R. Elbert, A. Laschewsky and H. Ringsdorf, J. Am. Chem.
Soc. 107, 4134-4141 (1985)). Copolymer films have also already been described (A. Laschewsky, H. Ringsdorf, G. Schmidt and J. Schneider, J. ~m. Chem. Soc. 109, 788-796 (1987)). In these copolymers, one of the comonomers carries at least one long alkyl chain, while .: . ~ : :
: , 2~325 -the second monomer is water-soluble, or carries at least - polar and hydrophilic groups. If such polymer films are intended to be used as resist materials, such as, for example, described by R. Jones, C.S. Winter, R.H. Tredgold, P. Hodge and A. Hoorfar, Polymer 28, 1619-1626 (1987), the problem of insufficient etching stability of these films during plasma etching arises.
However, it is known from resist technology that the etching stability of photoresists in an oxygen plasma can be drastically increased by incorporating silicon com-pounds. Thus, aliphatic and~or aromatic hydroxyl-carrying polymeric binders have been described which contain silanyl groups in the side chain which, as components of a photosensitive mixture, give this mixture increased resistance to plasma etching ~EP-A-0,337,188). The photosensitive layer, which is formed by spin-coating the substrate with a resist solution containing such a binder and compounds from the class of compounds of o-quinone diazides, has a layer thickness of 0.3 to 10 ~m. A
disadvantage for microelectronic applications, for example high-resolution electron beam lithography, is the relatively high layer thickness of resist films of this type.
Furthermore, Langmuir-Blodgett layers of amphiphilic polysiloxanes are known (Adv. Mater. 3 (1991), 27). It is true that they have good etching resistance in an oxygsn plasma, but for many applications they have only insuffi-cient temperature resistance, owing to the siloxane main chain.
Accordingly, the object is to prepare polymers from which Langmuir-Blodgett films can be formed which have improved resistance to temperature and plasma etching.
The in~ention relates to amphiphilic copolymers contain-ing silanyl groups and structural units derived from at least one monomer of the formula I
: -2~ 32~
~ _ 3 -O Y
A-Bn-tCH~m-X-~-c- CH2 (I) and at least one monomer of the formula II
OY
D-E-L-C-C - CH2 ( I I ) in which A- is CH3- or CF3-, -B- is -CH2- or -CF2-, n is an integer from 5 to 25, m is an integer from ~ero to 12, -X- is -O-, -NR1- or -Z-, in which R~- is H-, CH3-(CH2)n- or CF3-(CF2)n-(CH2)~--Z- is -X'-(CH2)p-X' or O O
. ~
-X'-C-(CH2),-C-X'-(CH2)p-X', p is an integer from 2 to 10, l is an integer from 1 to 10 and -X'- is -O- or -NR~
-Y is -H, -CH3, -CN, -Cl, -Br or -F, -D is -SiR2(SiR23)2, Si(SiR23)3, -SiR22-SiR23 or -(SiR22)2-SiR23, in which R2 is C,-C3-alkyl, -E- is Cl-C4-alkylene and O
-L- is -o-~-NRl-~-NH-c-x~-(cH2)p-xl- or -NH-C-(O-CH2-C:~2)p-O- ist.
Preferred structural units derived from monomers of the formula I carry only one long side chain, i.e. the function group -~-, which is:-O-, -NH- or -Z- and -X'-g which is -O- or -NH-.
', :
" 2~6~32~
Preferred structural units deri~ed from monomers of the formula II are those in which -D is -(SiR2~-SiRZ3 and R2 is C'1-C3-alkyl, in particular methyl, -E- is C2-alkylene, p -L- is -NH- or -NH-C-O-cH2-cH2-O- and -Y is -H or -CH3.
The synthesis of the monomers of the formula I can be carried out by known methods ~y reaction of a vinylcar-boxylic acid or an activated derivative of this car-boxylic acid, for example an acid halide, with a long-chain alcohol or amine of the formula IV
A - Bn - (CH2)~ - X' - H (IV) in which A-, -B-, -X'-, m and n have the abovementioned meaning.
Monomers o~ the formula I containing structural units Z
can be prepared first by reaction of a dicarboxylic acid of the formula (V) HOOC - (CH2)l - COOH (V~
or of an activated derivative of this dicarboxylic acid, such as, for example, of an acid anhydride, an ester or an acid halide, with an unsaturated alcohol or amine of the formul~ (VI) Y O
- CH2 = C - C - X' - (CH~)p - X' - H (VI) in which 1, p, Y and X' have the abovementioned meaning, to give the monoester, followed by condensation with a long-chain alcohol or amine of the formula VII
- . . :.
.
2~6132~
A - Bn - (CH2)m - X' H (VII) in which A, B, X', n and m have the abovementioned meaning.
However, they can also be prepared by the reverse reac-tion sequence, i.e. by reaction of the dicarboxylic acid of the formula (V) or of one of its reackive derivatives with a long-chain alcohol or am:ine of the formula (VII), followed by esterification of the intermediate with the unsaturated alcohol of the formula (VI).
The monomers containing silanyl groups of the formula II
can be prepared by reaction of a vinylcarboxylic acid or of an activated derivative thereof with a silylating reagent of the formula VIII
D - E - L' - H (VIII) in which -L'- is -NR1 or -O-, and Rl, D and L have the abovementioned meaning.
Silylating reagents of the formula VIII are described in EP-A-0,336,276.
The monomers of the formula II can furthermore be syn-thesized by reaction of isocyanato-containing silylating reagents of the formula IX
D - E - N = C = O (IX) in which D and E have the abovementioned meaning, with an unsaturated alcohol or amine of the formula VI or of the formula X
.
. .: -- . : . . . : . ~ : .
2~3~5 CH2 = C-C- O-(~H2-CH2-O)p~H (X) Y O
Copolymers (i.e. ter- and multipolymers) which in addi-tion to the structural units derived from monomers of formula I and II contain at least one structural unit derived from further functional comonomers, for example those leading to radiation-induced crosslinking of the polymers, are also suitable ~or the purposes of the invention. Further comonomers are also monomers having long alkyl chains, for example monomers such as described by Jones et al., Elbert et al. and Laschewsky et al. in the abovementioned publication~ and in WO 83/03165.
Moreover, hydrophilic, preferably water-soluble, vinyl monomers, such as, for example, itaconic acid, fumaric acid, maleic acid, acrylic acid, cyanoacrylic acid and methacrylic acid or derivatives thereof are suitable as comonomers.
Particular preference is given to those comonomers carry-ing radiation-crosslinkable units.
The proportion of structural units derived from silanyl-containing monomers of the formula II in the copolymercan be 5 to 98, preferably 30 to 85 and in particular 30 to 70, mol ~. The proportion of structural units derived from monomers of the formula I in the copolymer can be 95 to 2, preferably 70 to 15 and in particular 70 to 30, mol %, the proportions of the structural units adding up to a total of lO0 mol %.
In copolymers containing structural units derived from at least one mon~mer each of the formula I and II and at least one further functional comonomer, preferably containing a radiation-crosslinkable unit, the propor~ion of structural units derived from monomers of the formula I can be 90 to 5, preferably 60 to 20, mol %, the proportion of structural units derived from monomers of - ~ , , ::
:
3 ~ ~
the formula II can be 5 to 90, prefera~ly 20 to 60, mol %, and the proportion of structural units derived from further functional comonomers can be 5 to 60, preferably 20 to 40, mol ~, 1he proportions of the structural units adding up to a total of 100 mol %.
The polymerization is preferably carried out as a free-radical polymerization with the addition of a freP-radical initiator using con~entional methods.
The polymers or films according to the invention can also be mixed with further appropriate components, for e~ample with dyes, amphiphilic crosslinking agents, monomeric or polymeric amphiphiles. The proportion of these additives in such mixtures can be 1 to 80 ~ by weight.
The films are prepared according to the invention by dissolving the organic polymers or mixtures containing preferably 10 - 100 % by weight of the polymers according to the invention in a substantially volatile, water-immiscible solvent and placing (= spreading) them on the surface of an aqueous solution in a film balance.
The average area per repeating unit is calculated from the dLmension of the surface, the spreading volume and the concentration of the solution. Phase transitions during compression of the molecules can ~e monitored via the force/area isotherm.
The molecules are compressed by means of a barriex, as a result of which the alkyl chains are aligned substantial-ly perpendicular to the boundary layer with increasing surface density. During compression, a highly ordered monomolecular film, whose constant layer thickness is substantially determined by the chain length of the alkyl side chain of the polymers and their tilting angle (i.e.
the angle at which the molecular chains on the water surface are tilted with respect to the normal) is formed at the bounda~ layer through self-organization of the molecules. The typical thickness of such a film is -- 8 - 206~2~
0.5 - ~ nm.
~t a constant pressure, the film is removad from the water surface by immersion or withdrawal of a suitable substrate with retention of the order.
In most cases, the subphase used for the monofilm preparation is ~ater or aqueous solutions. However, other liquids having a high surface tension, such as, for example, glycerol, glycol, dimekhyl sulfoxide, dimethyl-formamide or acetonitrile can also be used.
Suitable substrates are any solid, preferably dimen-sionally stable, substrates made of a variety of mater-ials. The substrates which serve as support can be, for example, transparent or op~que, electrically conducting or insulating. The substrate can be hydrophobic or hydrophilic. The surface of the substrate to which the LB
layer is applied can have been made hydrophobic. The surface of the substrate to be coated should be as pure as possible so as not to disturb formation of a thin ordered layer. The presence of surface-active substances on the surface of the substrates to be coated can in particular impair preparation of the layer. It i5 possible to provide the substrates serving as support with an intermediate layer on the surface to be coated before applying the LB films, in order to improve, for ~5 example, adhesion of the film to the substrate.
Examples of materials which can be used for the sub-- strates are metals, such as, for example, gol , platinum, nickel, palladium, aluminum, chromium, niobium, tantalum, titanium, steel and the like. Further suitable materials for the substrates are plastics, such ast for example, polyesters, for example polyethylene terephthaIate or polybutylene terephthalate, polyvinyl chloride, poly-vinylidene chloride, polytetrafluoroeth~lene, poly-styrene, polyethylene or polypropylene.
.
--` 2~13~
g In particular semiconductors, such afi silicon, germanium or gallium arsenide or else glass, silicon dioxide, ceramic materials or cellulose products are suitable for the substrates. If required, the surface of glass and other hydrophilic substrates can be made hydrophobic in a manner known per se by reaction with alkylsilanes or hexamethyldisilazanes. The selection of the substrate materials depends primarily on the intended application of the layer elements according to the invention. ~s a rule, for optical elements, transparent substrates are used as supports. If the layer elements according to the invention are used, for example, in electronics or in electrochemical processes, the substrates used are in particular electrically conducting materials, such as metal or metallic surface layers, for example on plastic sheets or glass.
The substrates which serve as carriers for the films according to the invention can, depending on the par-ticular application, have any desired form. For example, 2D they can be in the form of films, sheets, slabs, tapes or even cylinders or can be selected from other forms. I~
general, the supports will be flat planar substrates, such as, for example, films, sheets, slabs, tapes and the like. The surface of the substrates to be coated i5 preferably smooth, as is customary for the preparation of ~B films. In the case of flat planar substrates, the films according to the invention can be applied to one or both surfaces of the substrate.
The multi-layer structure which can be readily prepared from the polymers according to the invention is distin-guished by a small number of defects and good temperature and etching resistance.
Such films on substrates are suitable, for example, for optical waveguide or for the production of filters for optical purposes. Substrates containing films prepared from copolymers according to the invention, which contain .
' ,: ' 2~132~
radiationcrosslinkable units, are also used for lithographic purposes. Owing to the low critical surface tension, the film~ are also suitable for improving the friction properties of materials and for the production of protective layers.
The invention is illustrated in more detail by the examples which follow. The solvents used for the synthesis of the monomers are dried by conventional methods (for example by molecular sieve~. The polymeriza-tions are carried out in an inert gas atmosphere, forexample of nitrogen.
Example 1: Synthesis of the disilane monomer 1 CH3 C:H3 o CH3 - Si - Si - CH2 - CH2-NH2 + CH2 = CH - C - Cl _N(C2H~2Q3 CH3 CH3 o CH3 - Si - Si - CH2 - CH2 -NH - C - CH = CH2 (1) I HCI
5.8 g of 2-pentamethyldisilylethylamine hydrochloride are dissolved in about 100 ml of dichloromethane and ex-tracted twice by shaking with 100 ml each of 2 M NaOH.The organic phase is dried with Na2SO4, and the solvent is removed in vacuo. 50 mg of 2,6-di-tert.-butyl-p cresol are added to the remaining clear liquid, and the mixture is dissolved in 40 ml of anhydrous tetrahydrofuran (dichloromethane, dioxane and toluene are also suitable solvents), the solution is cooled to 2C, 4.5 ml of anhydrous triethylamine are added, and 2.7 ml of acryloyl chloride, dissolv~d in 30 ml of anhydrous tetrahydro-furan, are metered in at 2C over a period of 30 minutes.
The ice bath :is then removed, and the reaction mixture, after reaching a temperature of 20 - 25C, is stirred for .
' : --:
-, .. ~; : :
2 ~
another 2 hours. The reaction mixture~ after addition of 100 ml of dichloromethane, is then e~tracted twice with 50 ml each of 1 M HCl, the organic phase is dried with Na2SO4 and the solvent is removed in vacuo. The remaining solid is purified by recrystallization from n-hexane, giving 4.95 g (80 % of theory) of a white powder.
H NMR (100 MHz, CDCl3):
= -0.1 - 0.1 (m, 15H, Si-CH3) ~ O . 7 - 1.0 (m, 2H, SiCH2), 3.1 - 3.5 (m, 2H, N-CH2), 5.2 - 5.8 (m, 2H
-NH- and =CH-CO), 5.8 - 6.4 (m, 2H, =CH2).
Example 2: Synthesis of the disilane monomer 2 CH3 CH3 H3C O ~A~)J
CH3-Si-Si-CH2-CH2-NCO + CH2= C-C-O-CH2-C:H2-OH .
CHs CH3 CH3 pH3 O CH3 CH3 - Si - Si - CH2 - CH2 - NH - ~ - O - CH2 - CH2 - O - C - C = CH2 (2) 6.04 g of the disilane isocyanate are dissolved together with 35 mg of 1,4-diazabicyclo[2.2.2]octane in 50 ml of dichloromethane. The solution is cooled in an ice/sodium chloride bath to 0C, and a mixture of 4.25 ml of 2-hydroxyethyl methacrylate, 5 mg of 2,6-di-tert.-butyl-p-cresol and 25 ml of dichloromethane is metered in over a period of 15 minutes. After addition is complete, the reaction mixture is heated to the boiling temperature over a period of 30 minl~tes, and boiled at the boiling temperature for 20 hours. After cooling to a temperature of 20 - 25DC, the reaction mixture is extracted twice by shaking with 100 ml each of 1 M HCl and water, the organic phase is dried with Na2SO4, and the solvent i~
removed in vacuo. 50 mg of 2,6-di-tert.-butyl-p-cresol are added to the remaining oily substance, and the 206~ 3?,~
mixture is purified by column chromatography (eluent:
n-hexane/ethyl acetate 3:1 (volume ratio)). This gives 15 g (65 % of theory) of a colorless oil.
lH NMR ( 100 MHz , CDCl3):
~ = -0.1 - 0.1 (m~ 15H, Si ('H3), O . 7 - 1. O (m, 2H, SiCH2), 1.7 - 1.9 (m, 3H, C-CH3~, 3.1 - 3.5 (m, 2H, N-CHz), 4.2 - 4.3 (s, 4H, O-CH2-CH2-O~CO), 4.4 - 4.7 (m, lH, NH), 5.4 - 6.2 (m, 2H, =CH2).
Example 3: Free-radical copolymerization of the di~
silane monomer 1 with N-octadecylacrylamide 2.0 g of N-octadecylacrylamide and 0.622 g of the di-silane monomer 1 are dissolved in 20 ml of tetrahydro-furan, and 10.2 mg of azobisisobutyronitrile are added.
The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 -25C for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7 hours with continuous stirring (mag-netic stirxer). The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 -~5C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetxahydrofuran and precipit-ated ~y pouring into methanol, giving 1.9 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydrofuran. Determination of the molecu-lar weight by means of gel permeation chromatography gives an M~ of 4,800 and an M~ of 2,600 dalton (poly-styrene calibration). Elemental analysis (71.4 ~ by weight of C, 11.7 % by weight of X, 4.6 % by weight of N, 5.5 ~ by weight of O) gives a copolymer composition of 1 part of long-chain substituted monomer and 0.45 0.1 part of disilane monomer.
:
- . ~:
-- 2 ~ 2 5 Example 4: Free-radical copolymerization of the di-silane monomer i with N-octadecylacrylamide 2.0 g of N-octadecylacrylamide and 1.244 g of the di-silane monomer 1 are dissolved in 20 ml of tetrahydro-furan, and 10.2 mg of azobisisobutyronitrile are added.The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at room temperature for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetrahydrofuran and precipitated by pouring into methanol, giving 1.1 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydro-furan. Determination of the molecular weight by means ofgel permeation chromatography gives an M~ of 4,600 and an M~ of 2,500 dalton ~polystyrene calibration). Elemental analysis (68.4 % by weight of C, 11.1 % by weight of H, 4.9 % by weight of N, 5.4 % by weight of O~ gives a copolymer composition of 1 part of long-chain substituted monomer and 0.9 + 0.2 part of disilane monomer.
Example 5: Free-radical copolymerization of the di-silane monomer 1 with N-octadecylacrylamide 2.0 g of N-octadecylacrylamide and 2.49 g of the disilane monomer 1 are dissolved in 20 ml of tetrahydrouran, and 10.2 mg of azobisisobutyronitrile are added. The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 - 25C for one hour. The reaction mixture is then heated to the . ~ . ... .
- :, , ', , ~': , : ~
- 14 ~ 2~
boiling temperature and refluxed at the boiling tempsra-ture for 7 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to 20 - 25~C into methanol, and the product is filtered o~f with suction. In order to free it from residual monomer, it is dissolved two more tLmes in tetrahydrofuran and precipitated by pouring into methanol, giving 2.4 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydrofuran. ~etermination of the molecular weight by means of gel permeation chromatography gives an N~ o~ 5,700 and an M~ of 4,300 dalton (polystyrene calibration). Elemental analysis (61.g ~ by weight of C, 11.1 % by weight of H, 5.4 % by weight of N) gives a copolymer composi~ion of 1 part of long-chain substituted monomer and 2.4 0.1 part of disilane monomer.
Example 6: Free-radical copolymerization of the di-silane monomer 1 with N-octadecylacrylamide 1.0 g of N-octadecylacrylamide and 3.11 g of the disilane monomer l are dissolved in 20 ml of tetrahydrofuran, and 5.1 mg of azobisisobutyronitrile are added. The solution is placed in a three-necked flask equipped with reflu~
condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 - 25C for one hour. ~he reaction mixture is then heated to the boiling temperature and refluxed at the boiling tempera-ture for 7 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetrahydrofuran and precipitated by pouring into meth-anol, giving 4.~ g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydro-furan. Determination of the molecular weight by means of gel permeation chromatography gives an M~ of 10,000 and .
--'- ' ,, ' . .
- . : '' '.': : ' - 15 _ 2~6~3~
an M~ of 6,~00 dalton (polystyrene calibration). Elemental analysis (57.8 % by weight of C, 10.6 % by weight of H, 5.6 % by weight of N) gives a copolymer composi~ion of 1 part of long-chain substituted monomer and 5.1 +
0.6 part of disilane monomer.
Example 7: Free-radical copolymerization of the di-silane monomer 2 with N-octadecylacrylamide O.g3 g of N-octadecylacrylamide and 0.50 g of the di-silane monomer 2 are dissolved in 30 ml of tetrahydro-furan, and 4.4 mg of azobisisobutyronitrile are added.The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 -25C for one hour. The reaction mixture is then heatedto the boiling temperature and refluxed at the boiling temperature for 6 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetrahydrofuran and precipit-ated by pouring into methanol, giving 0.58 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydrofuran. Determination of the molecu-lar weight by means of gel permeation chromatographygives an N~ of 5,400 and an M~ of 2,500 dalton (poly-styrene calibration). Elemental analysis ~65.2 % by weight of C~ 10.3 ~ by weight of H, 4.2 % by weight of N~
gives a copolymer composition of 1 part of long-chain substituted monomer and 1.3 + 0.3 part of disilane monomer.
Example 8: Free-radical copolymeri~ation of the di-silane monomer 2 with N-octadecylacrylamide 0.93 g of N-octadecylacrylamide and O.g9 g of the di-silane monomer 2 are dissolved in 30 ml of :~ - ~ , . -. - .
2~32~
tetrahydrofuran, and 4.4 mg of azobisi~obutyronitrile are added. The solution is placed in a three-necked flask eguipped with reflux condenser twith gas-discharge tube and bubble counter), thermometler and gas introduction tube, and the mixtu:re is flushed with nitrogen at a temperature of 20 - 25C for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7.5 hours with continuous stirring. Tha polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in hot tetrahydrofuran and precipitated by pouring into methanol, giving 0.46 g of a white fine-particle material which is insoluble in methanol and soluble in hot tetrahydrofuran.
Determination of the molecular weight by means of gel permeation chromatography could not be carried out, due to the low solubility at 20C. Elemental analysis (62.1 ~
by weight of C, 10.5 ~ by weight of H, 4.1 ~ by weight of N) gives a copolymer composition of 1 part of long-chain substituted monomer and 1.3 i 0.1 part of disilane monomer.
Example 9: Free-radical copolymerization of the di silane monomer 2 with N-octadecylacrylamide 0.93 g of N-octadecylacrylamide and 1.99 g of the di-silane monomer 2 are dissolved in 30 ml of tetrahydro-furan, and 4.4 mg of azobisisobutyronitrile are added.
The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 -25C for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7.5 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and .
.
- :
, 2~3~
the product is filtered off with suc~ion. In order to free it from residual monomer, it is dissolved two more times in hot tetrahydrofuran and precipitated by pouring into methanol, giving 1.0 g of a white fine-particle material which is insoluble in methanol and soluble in hot tetrahydrofuran. Determination of the molecular weight ~y means of gel permeation chromatography could not be carried out, due to the low solubility at 20C.
Elemental analysis (59.0 % by weight of C, 10.0 % by weight of H, 4.39 % by weight of N) gives a copolymer composition of 1 part of long-chain substituted monomer and 1.9 + 0.4 part of disilane monomer.
Example 10: Film preparation by the Langmuir-Blodgett method A microscope slide made of glass (76 mm x 26 mm) is cleaned by the following method:
The glass is placed in a freshly prepared mixture of four parts of conc. H2S04 and one part of 30 ~ Hz02, whose temperature i8 60C, for one hour, rinsed off with water of high purity and cleaned in an alkaline, ~urfactant-free cleaning solution, for example ~Extran AP 11 (conc.
2 - 4 g/l) for 15 minutes at a temperature of 50C by means of ultrasound. The glass is then thoroughly rinsed with water of high purity (18 mohm, free of particles) and dried in a warm air stream. The glass is then made hydrophobic by treating it with hexamethyldisilazane vapor (for 10 minutes at a temperature of 70C).
Multilayers comprising the polymer prepared in Example 3 are transferred by the Langmuir and Blodgett method to the glass support by spreading 0.2 cm3 of a solution of 9.3 mg of the polymer in 10 cm3 of a 9:1 (volume ratio) mixture of methylene chloride and tetrahydrofuran on an aqueous subphase at a subphase temperature of 10C in a Langmuir film balance. By reducing the monofilm-covered water surface, the pressure is adjusted to 20 mN/m and .
3 2 ~
kept constant at this value. The support is now Lmmersed perpendicularly from above through the water surface into the film balance (Lmmersion rate: 20 mm/min.) and after a short pause (10 sec.) at the lower turnaround point again withdrawn (withdrawal xate: 20 mm/min.). Each immersion and also each withdrawal process transfers one monolayer to the support. By repeating the dipping process several times after a wait of one minute each at the upper turnaround point, a total of 10 double layers are transferred. The transfer ratios are around 90 %.
Even when 50 and more monolayers are transferred, optically clear, transparent films are obtained.
Films are also obtained from the polymers prepared in Examples 4, 5 and 6, using the same procedure. The transfer conditions for these polymers are as follows:
Polymer from Example: 4 5 6 Subphase temperature: 10C 10C 10C
Pressure: 20 mN/m 20 mN/m 20 mN/m Transfer ratio: 90 ~ 70 ~ 80 %
Example 11: Ellipsometric measurements of the layer thickness and the refractive index Silicon chips (40 mm x 10 mm3 are cut from a silicon wafer and cleaned as follows:
1. Treatment for 1 hour in a freshly prepared mixture comprising one part of 30 ~ H2O2 and four parts of conc. H2SO4 whose temperature is 60C. They are then rinsed with water of high purity.
2. Immersion in an NH4F-buffered HF solution for 30 seconds, followed again by rinsing using water of high purity. After this trea~ment, the silicon chips are hydrophobic (contact angle with water: 75C).
Layers made from the polymers prepaxed in Examples 3, 4, . ~ ' ' ' ' .
~' .
~.
2~3~
.
and 6 are transferred to the silicon chip by the Langmuir and Blodgett method under the same conditions as in Example 10. Specimens containing 10, 30, 50 and 70 monolayers, respectively, of the individual polymers are prepared, and the layer thicknesses and the refract-ive index of the LB films are measured ellipsometrically.
Results of the measurements:
Polymer from Example: 3 4 5 6 Refractive index at 633 nm: 1.499 1.486 1.454 1.477 Layer thickness in nm/monolayer: 1.990 1.460 0.698 0.830 Example 12: Measurements of heat stability Silicon chips (40 mm x 10 mm) are cut from a thermally oxidized silicon wafer (thic~ness of the oxide layer:
160 nm) and placed in a freshly prepared mixture comprising one part of 30 ~ H2O2 and four parts of conc.
H2SO4 at a temperature of 60C for one hour. After thor-ough rinsing using water of high purity, the chip istreated in an ultrasound bath with an alkaline, surfact-ant-free cleaning solution, for example ~Extran AP 11 (conc. 2 - 4 g~l) at a temperature of 50DC for 15 min-utes, thoroughly rinsed with water of high purity and dried in a warm air stream. It is then made hydrophobic by means of a treatment with hexamethyldisilazane vapour (10 minutes at a temperature of 70C).
Coating by the LB method with 8 monolayers each is carried out as described in Example 10, using the poly-mers prepared :in Examples 3, 4, 5 and 6.
The coated carrier is heated in a special apparatus at alinear temperature gradient (0.5C/sec.3. During the heating-up process, the thickness of the LB film is - ,: , ;. . . . . :
. : : . ' . ` . . -. . ~
- .
.- . ~
2~13~
measured by the intensity of a perpendicularly polarized laser beam (633 nm) reflected by the specimen. The temperature at which the first c:hange in layer thickness takes place is 140C in layerls made from the polymer prepared in Example 3, 130C in layers made from the polymer prepared in Example 4, :L20C in layers made from the polymer prepared in Example 5, and 130C in layers made from the polymer prepared in Example 6. (For comparison: in LB layers made from 22-tricosenic acid, this temperature is 70C.) Example 13: Measurements of the critical surface tension Silicon chips (40 mm x 10 mm) are cleaned as in Example 11 and coated as in Example 11 with eight mono-layers each made from the polymers prepared inExamples 3, 4, 5 and 6. Droplets of a li~uid from the series of n-alkanes (C~H2~ - C,6H34) are placed on the surface of the transferred layers, and the contact angles of the droplets with the surface are measured. The critical surface tension is determined from these contact angles by the method of Zisman (W.A. Zisman, Adv. Chem.
Ser., 43 (1964), 1-51 and Phys. Chem. Surfaces, A.W. Adamson, New York 1982). The following values are found. -Polymer from ExampleCrit. surface tension [mN~m]
3 21.7 4 23.8 25.2 6 25.2 (For comparison: A polyethylene surface gives a value of 31 mN/m in this measurement).
' ~
the formula II can be 5 to 90, prefera~ly 20 to 60, mol %, and the proportion of structural units derived from further functional comonomers can be 5 to 60, preferably 20 to 40, mol ~, 1he proportions of the structural units adding up to a total of 100 mol %.
The polymerization is preferably carried out as a free-radical polymerization with the addition of a freP-radical initiator using con~entional methods.
The polymers or films according to the invention can also be mixed with further appropriate components, for e~ample with dyes, amphiphilic crosslinking agents, monomeric or polymeric amphiphiles. The proportion of these additives in such mixtures can be 1 to 80 ~ by weight.
The films are prepared according to the invention by dissolving the organic polymers or mixtures containing preferably 10 - 100 % by weight of the polymers according to the invention in a substantially volatile, water-immiscible solvent and placing (= spreading) them on the surface of an aqueous solution in a film balance.
The average area per repeating unit is calculated from the dLmension of the surface, the spreading volume and the concentration of the solution. Phase transitions during compression of the molecules can ~e monitored via the force/area isotherm.
The molecules are compressed by means of a barriex, as a result of which the alkyl chains are aligned substantial-ly perpendicular to the boundary layer with increasing surface density. During compression, a highly ordered monomolecular film, whose constant layer thickness is substantially determined by the chain length of the alkyl side chain of the polymers and their tilting angle (i.e.
the angle at which the molecular chains on the water surface are tilted with respect to the normal) is formed at the bounda~ layer through self-organization of the molecules. The typical thickness of such a film is -- 8 - 206~2~
0.5 - ~ nm.
~t a constant pressure, the film is removad from the water surface by immersion or withdrawal of a suitable substrate with retention of the order.
In most cases, the subphase used for the monofilm preparation is ~ater or aqueous solutions. However, other liquids having a high surface tension, such as, for example, glycerol, glycol, dimekhyl sulfoxide, dimethyl-formamide or acetonitrile can also be used.
Suitable substrates are any solid, preferably dimen-sionally stable, substrates made of a variety of mater-ials. The substrates which serve as support can be, for example, transparent or op~que, electrically conducting or insulating. The substrate can be hydrophobic or hydrophilic. The surface of the substrate to which the LB
layer is applied can have been made hydrophobic. The surface of the substrate to be coated should be as pure as possible so as not to disturb formation of a thin ordered layer. The presence of surface-active substances on the surface of the substrates to be coated can in particular impair preparation of the layer. It i5 possible to provide the substrates serving as support with an intermediate layer on the surface to be coated before applying the LB films, in order to improve, for ~5 example, adhesion of the film to the substrate.
Examples of materials which can be used for the sub-- strates are metals, such as, for example, gol , platinum, nickel, palladium, aluminum, chromium, niobium, tantalum, titanium, steel and the like. Further suitable materials for the substrates are plastics, such ast for example, polyesters, for example polyethylene terephthaIate or polybutylene terephthalate, polyvinyl chloride, poly-vinylidene chloride, polytetrafluoroeth~lene, poly-styrene, polyethylene or polypropylene.
.
--` 2~13~
g In particular semiconductors, such afi silicon, germanium or gallium arsenide or else glass, silicon dioxide, ceramic materials or cellulose products are suitable for the substrates. If required, the surface of glass and other hydrophilic substrates can be made hydrophobic in a manner known per se by reaction with alkylsilanes or hexamethyldisilazanes. The selection of the substrate materials depends primarily on the intended application of the layer elements according to the invention. ~s a rule, for optical elements, transparent substrates are used as supports. If the layer elements according to the invention are used, for example, in electronics or in electrochemical processes, the substrates used are in particular electrically conducting materials, such as metal or metallic surface layers, for example on plastic sheets or glass.
The substrates which serve as carriers for the films according to the invention can, depending on the par-ticular application, have any desired form. For example, 2D they can be in the form of films, sheets, slabs, tapes or even cylinders or can be selected from other forms. I~
general, the supports will be flat planar substrates, such as, for example, films, sheets, slabs, tapes and the like. The surface of the substrates to be coated i5 preferably smooth, as is customary for the preparation of ~B films. In the case of flat planar substrates, the films according to the invention can be applied to one or both surfaces of the substrate.
The multi-layer structure which can be readily prepared from the polymers according to the invention is distin-guished by a small number of defects and good temperature and etching resistance.
Such films on substrates are suitable, for example, for optical waveguide or for the production of filters for optical purposes. Substrates containing films prepared from copolymers according to the invention, which contain .
' ,: ' 2~132~
radiationcrosslinkable units, are also used for lithographic purposes. Owing to the low critical surface tension, the film~ are also suitable for improving the friction properties of materials and for the production of protective layers.
The invention is illustrated in more detail by the examples which follow. The solvents used for the synthesis of the monomers are dried by conventional methods (for example by molecular sieve~. The polymeriza-tions are carried out in an inert gas atmosphere, forexample of nitrogen.
Example 1: Synthesis of the disilane monomer 1 CH3 C:H3 o CH3 - Si - Si - CH2 - CH2-NH2 + CH2 = CH - C - Cl _N(C2H~2Q3 CH3 CH3 o CH3 - Si - Si - CH2 - CH2 -NH - C - CH = CH2 (1) I HCI
5.8 g of 2-pentamethyldisilylethylamine hydrochloride are dissolved in about 100 ml of dichloromethane and ex-tracted twice by shaking with 100 ml each of 2 M NaOH.The organic phase is dried with Na2SO4, and the solvent is removed in vacuo. 50 mg of 2,6-di-tert.-butyl-p cresol are added to the remaining clear liquid, and the mixture is dissolved in 40 ml of anhydrous tetrahydrofuran (dichloromethane, dioxane and toluene are also suitable solvents), the solution is cooled to 2C, 4.5 ml of anhydrous triethylamine are added, and 2.7 ml of acryloyl chloride, dissolv~d in 30 ml of anhydrous tetrahydro-furan, are metered in at 2C over a period of 30 minutes.
The ice bath :is then removed, and the reaction mixture, after reaching a temperature of 20 - 25C, is stirred for .
' : --:
-, .. ~; : :
2 ~
another 2 hours. The reaction mixture~ after addition of 100 ml of dichloromethane, is then e~tracted twice with 50 ml each of 1 M HCl, the organic phase is dried with Na2SO4 and the solvent is removed in vacuo. The remaining solid is purified by recrystallization from n-hexane, giving 4.95 g (80 % of theory) of a white powder.
H NMR (100 MHz, CDCl3):
= -0.1 - 0.1 (m, 15H, Si-CH3) ~ O . 7 - 1.0 (m, 2H, SiCH2), 3.1 - 3.5 (m, 2H, N-CH2), 5.2 - 5.8 (m, 2H
-NH- and =CH-CO), 5.8 - 6.4 (m, 2H, =CH2).
Example 2: Synthesis of the disilane monomer 2 CH3 CH3 H3C O ~A~)J
CH3-Si-Si-CH2-CH2-NCO + CH2= C-C-O-CH2-C:H2-OH .
CHs CH3 CH3 pH3 O CH3 CH3 - Si - Si - CH2 - CH2 - NH - ~ - O - CH2 - CH2 - O - C - C = CH2 (2) 6.04 g of the disilane isocyanate are dissolved together with 35 mg of 1,4-diazabicyclo[2.2.2]octane in 50 ml of dichloromethane. The solution is cooled in an ice/sodium chloride bath to 0C, and a mixture of 4.25 ml of 2-hydroxyethyl methacrylate, 5 mg of 2,6-di-tert.-butyl-p-cresol and 25 ml of dichloromethane is metered in over a period of 15 minutes. After addition is complete, the reaction mixture is heated to the boiling temperature over a period of 30 minl~tes, and boiled at the boiling temperature for 20 hours. After cooling to a temperature of 20 - 25DC, the reaction mixture is extracted twice by shaking with 100 ml each of 1 M HCl and water, the organic phase is dried with Na2SO4, and the solvent i~
removed in vacuo. 50 mg of 2,6-di-tert.-butyl-p-cresol are added to the remaining oily substance, and the 206~ 3?,~
mixture is purified by column chromatography (eluent:
n-hexane/ethyl acetate 3:1 (volume ratio)). This gives 15 g (65 % of theory) of a colorless oil.
lH NMR ( 100 MHz , CDCl3):
~ = -0.1 - 0.1 (m~ 15H, Si ('H3), O . 7 - 1. O (m, 2H, SiCH2), 1.7 - 1.9 (m, 3H, C-CH3~, 3.1 - 3.5 (m, 2H, N-CHz), 4.2 - 4.3 (s, 4H, O-CH2-CH2-O~CO), 4.4 - 4.7 (m, lH, NH), 5.4 - 6.2 (m, 2H, =CH2).
Example 3: Free-radical copolymerization of the di~
silane monomer 1 with N-octadecylacrylamide 2.0 g of N-octadecylacrylamide and 0.622 g of the di-silane monomer 1 are dissolved in 20 ml of tetrahydro-furan, and 10.2 mg of azobisisobutyronitrile are added.
The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 -25C for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7 hours with continuous stirring (mag-netic stirxer). The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 -~5C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetxahydrofuran and precipit-ated ~y pouring into methanol, giving 1.9 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydrofuran. Determination of the molecu-lar weight by means of gel permeation chromatography gives an M~ of 4,800 and an M~ of 2,600 dalton (poly-styrene calibration). Elemental analysis (71.4 ~ by weight of C, 11.7 % by weight of X, 4.6 % by weight of N, 5.5 ~ by weight of O) gives a copolymer composition of 1 part of long-chain substituted monomer and 0.45 0.1 part of disilane monomer.
:
- . ~:
-- 2 ~ 2 5 Example 4: Free-radical copolymerization of the di-silane monomer i with N-octadecylacrylamide 2.0 g of N-octadecylacrylamide and 1.244 g of the di-silane monomer 1 are dissolved in 20 ml of tetrahydro-furan, and 10.2 mg of azobisisobutyronitrile are added.The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at room temperature for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetrahydrofuran and precipitated by pouring into methanol, giving 1.1 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydro-furan. Determination of the molecular weight by means ofgel permeation chromatography gives an M~ of 4,600 and an M~ of 2,500 dalton ~polystyrene calibration). Elemental analysis (68.4 % by weight of C, 11.1 % by weight of H, 4.9 % by weight of N, 5.4 % by weight of O~ gives a copolymer composition of 1 part of long-chain substituted monomer and 0.9 + 0.2 part of disilane monomer.
Example 5: Free-radical copolymerization of the di-silane monomer 1 with N-octadecylacrylamide 2.0 g of N-octadecylacrylamide and 2.49 g of the disilane monomer 1 are dissolved in 20 ml of tetrahydrouran, and 10.2 mg of azobisisobutyronitrile are added. The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 - 25C for one hour. The reaction mixture is then heated to the . ~ . ... .
- :, , ', , ~': , : ~
- 14 ~ 2~
boiling temperature and refluxed at the boiling tempsra-ture for 7 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to 20 - 25~C into methanol, and the product is filtered o~f with suction. In order to free it from residual monomer, it is dissolved two more tLmes in tetrahydrofuran and precipitated by pouring into methanol, giving 2.4 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydrofuran. ~etermination of the molecular weight by means of gel permeation chromatography gives an N~ o~ 5,700 and an M~ of 4,300 dalton (polystyrene calibration). Elemental analysis (61.g ~ by weight of C, 11.1 % by weight of H, 5.4 % by weight of N) gives a copolymer composi~ion of 1 part of long-chain substituted monomer and 2.4 0.1 part of disilane monomer.
Example 6: Free-radical copolymerization of the di-silane monomer 1 with N-octadecylacrylamide 1.0 g of N-octadecylacrylamide and 3.11 g of the disilane monomer l are dissolved in 20 ml of tetrahydrofuran, and 5.1 mg of azobisisobutyronitrile are added. The solution is placed in a three-necked flask equipped with reflu~
condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 - 25C for one hour. ~he reaction mixture is then heated to the boiling temperature and refluxed at the boiling tempera-ture for 7 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetrahydrofuran and precipitated by pouring into meth-anol, giving 4.~ g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydro-furan. Determination of the molecular weight by means of gel permeation chromatography gives an M~ of 10,000 and .
--'- ' ,, ' . .
- . : '' '.': : ' - 15 _ 2~6~3~
an M~ of 6,~00 dalton (polystyrene calibration). Elemental analysis (57.8 % by weight of C, 10.6 % by weight of H, 5.6 % by weight of N) gives a copolymer composi~ion of 1 part of long-chain substituted monomer and 5.1 +
0.6 part of disilane monomer.
Example 7: Free-radical copolymerization of the di-silane monomer 2 with N-octadecylacrylamide O.g3 g of N-octadecylacrylamide and 0.50 g of the di-silane monomer 2 are dissolved in 30 ml of tetrahydro-furan, and 4.4 mg of azobisisobutyronitrile are added.The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 -25C for one hour. The reaction mixture is then heatedto the boiling temperature and refluxed at the boiling temperature for 6 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in tetrahydrofuran and precipit-ated by pouring into methanol, giving 0.58 g of a white fine-particle material which is insoluble in methanol and soluble in tetrahydrofuran. Determination of the molecu-lar weight by means of gel permeation chromatographygives an N~ of 5,400 and an M~ of 2,500 dalton (poly-styrene calibration). Elemental analysis ~65.2 % by weight of C~ 10.3 ~ by weight of H, 4.2 % by weight of N~
gives a copolymer composition of 1 part of long-chain substituted monomer and 1.3 + 0.3 part of disilane monomer.
Example 8: Free-radical copolymeri~ation of the di-silane monomer 2 with N-octadecylacrylamide 0.93 g of N-octadecylacrylamide and O.g9 g of the di-silane monomer 2 are dissolved in 30 ml of :~ - ~ , . -. - .
2~32~
tetrahydrofuran, and 4.4 mg of azobisi~obutyronitrile are added. The solution is placed in a three-necked flask eguipped with reflux condenser twith gas-discharge tube and bubble counter), thermometler and gas introduction tube, and the mixtu:re is flushed with nitrogen at a temperature of 20 - 25C for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7.5 hours with continuous stirring. Tha polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and the product is filtered off with suction. In order to free it from residual monomer, it is dissolved two more times in hot tetrahydrofuran and precipitated by pouring into methanol, giving 0.46 g of a white fine-particle material which is insoluble in methanol and soluble in hot tetrahydrofuran.
Determination of the molecular weight by means of gel permeation chromatography could not be carried out, due to the low solubility at 20C. Elemental analysis (62.1 ~
by weight of C, 10.5 ~ by weight of H, 4.1 ~ by weight of N) gives a copolymer composition of 1 part of long-chain substituted monomer and 1.3 i 0.1 part of disilane monomer.
Example 9: Free-radical copolymerization of the di silane monomer 2 with N-octadecylacrylamide 0.93 g of N-octadecylacrylamide and 1.99 g of the di-silane monomer 2 are dissolved in 30 ml of tetrahydro-furan, and 4.4 mg of azobisisobutyronitrile are added.
The solution is placed in a three-necked flask equipped with reflux condenser (with gas-discharge tube and bubble counter), thermometer and gas introduction tube, and the mixture is flushed with nitrogen at a temperature of 20 -25C for one hour. The reaction mixture is then heated to the boiling temperature and refluxed at the boiling temperature for 7.5 hours with continuous stirring. The polymer is precipitated by pouring the reaction solution cooled to a temperature of 20 - 25C into methanol, and .
.
- :
, 2~3~
the product is filtered off with suc~ion. In order to free it from residual monomer, it is dissolved two more times in hot tetrahydrofuran and precipitated by pouring into methanol, giving 1.0 g of a white fine-particle material which is insoluble in methanol and soluble in hot tetrahydrofuran. Determination of the molecular weight ~y means of gel permeation chromatography could not be carried out, due to the low solubility at 20C.
Elemental analysis (59.0 % by weight of C, 10.0 % by weight of H, 4.39 % by weight of N) gives a copolymer composition of 1 part of long-chain substituted monomer and 1.9 + 0.4 part of disilane monomer.
Example 10: Film preparation by the Langmuir-Blodgett method A microscope slide made of glass (76 mm x 26 mm) is cleaned by the following method:
The glass is placed in a freshly prepared mixture of four parts of conc. H2S04 and one part of 30 ~ Hz02, whose temperature i8 60C, for one hour, rinsed off with water of high purity and cleaned in an alkaline, ~urfactant-free cleaning solution, for example ~Extran AP 11 (conc.
2 - 4 g/l) for 15 minutes at a temperature of 50C by means of ultrasound. The glass is then thoroughly rinsed with water of high purity (18 mohm, free of particles) and dried in a warm air stream. The glass is then made hydrophobic by treating it with hexamethyldisilazane vapor (for 10 minutes at a temperature of 70C).
Multilayers comprising the polymer prepared in Example 3 are transferred by the Langmuir and Blodgett method to the glass support by spreading 0.2 cm3 of a solution of 9.3 mg of the polymer in 10 cm3 of a 9:1 (volume ratio) mixture of methylene chloride and tetrahydrofuran on an aqueous subphase at a subphase temperature of 10C in a Langmuir film balance. By reducing the monofilm-covered water surface, the pressure is adjusted to 20 mN/m and .
3 2 ~
kept constant at this value. The support is now Lmmersed perpendicularly from above through the water surface into the film balance (Lmmersion rate: 20 mm/min.) and after a short pause (10 sec.) at the lower turnaround point again withdrawn (withdrawal xate: 20 mm/min.). Each immersion and also each withdrawal process transfers one monolayer to the support. By repeating the dipping process several times after a wait of one minute each at the upper turnaround point, a total of 10 double layers are transferred. The transfer ratios are around 90 %.
Even when 50 and more monolayers are transferred, optically clear, transparent films are obtained.
Films are also obtained from the polymers prepared in Examples 4, 5 and 6, using the same procedure. The transfer conditions for these polymers are as follows:
Polymer from Example: 4 5 6 Subphase temperature: 10C 10C 10C
Pressure: 20 mN/m 20 mN/m 20 mN/m Transfer ratio: 90 ~ 70 ~ 80 %
Example 11: Ellipsometric measurements of the layer thickness and the refractive index Silicon chips (40 mm x 10 mm3 are cut from a silicon wafer and cleaned as follows:
1. Treatment for 1 hour in a freshly prepared mixture comprising one part of 30 ~ H2O2 and four parts of conc. H2SO4 whose temperature is 60C. They are then rinsed with water of high purity.
2. Immersion in an NH4F-buffered HF solution for 30 seconds, followed again by rinsing using water of high purity. After this trea~ment, the silicon chips are hydrophobic (contact angle with water: 75C).
Layers made from the polymers prepaxed in Examples 3, 4, . ~ ' ' ' ' .
~' .
~.
2~3~
.
and 6 are transferred to the silicon chip by the Langmuir and Blodgett method under the same conditions as in Example 10. Specimens containing 10, 30, 50 and 70 monolayers, respectively, of the individual polymers are prepared, and the layer thicknesses and the refract-ive index of the LB films are measured ellipsometrically.
Results of the measurements:
Polymer from Example: 3 4 5 6 Refractive index at 633 nm: 1.499 1.486 1.454 1.477 Layer thickness in nm/monolayer: 1.990 1.460 0.698 0.830 Example 12: Measurements of heat stability Silicon chips (40 mm x 10 mm) are cut from a thermally oxidized silicon wafer (thic~ness of the oxide layer:
160 nm) and placed in a freshly prepared mixture comprising one part of 30 ~ H2O2 and four parts of conc.
H2SO4 at a temperature of 60C for one hour. After thor-ough rinsing using water of high purity, the chip istreated in an ultrasound bath with an alkaline, surfact-ant-free cleaning solution, for example ~Extran AP 11 (conc. 2 - 4 g~l) at a temperature of 50DC for 15 min-utes, thoroughly rinsed with water of high purity and dried in a warm air stream. It is then made hydrophobic by means of a treatment with hexamethyldisilazane vapour (10 minutes at a temperature of 70C).
Coating by the LB method with 8 monolayers each is carried out as described in Example 10, using the poly-mers prepared :in Examples 3, 4, 5 and 6.
The coated carrier is heated in a special apparatus at alinear temperature gradient (0.5C/sec.3. During the heating-up process, the thickness of the LB film is - ,: , ;. . . . . :
. : : . ' . ` . . -. . ~
- .
.- . ~
2~13~
measured by the intensity of a perpendicularly polarized laser beam (633 nm) reflected by the specimen. The temperature at which the first c:hange in layer thickness takes place is 140C in layerls made from the polymer prepared in Example 3, 130C in layers made from the polymer prepared in Example 4, :L20C in layers made from the polymer prepared in Example 5, and 130C in layers made from the polymer prepared in Example 6. (For comparison: in LB layers made from 22-tricosenic acid, this temperature is 70C.) Example 13: Measurements of the critical surface tension Silicon chips (40 mm x 10 mm) are cleaned as in Example 11 and coated as in Example 11 with eight mono-layers each made from the polymers prepared inExamples 3, 4, 5 and 6. Droplets of a li~uid from the series of n-alkanes (C~H2~ - C,6H34) are placed on the surface of the transferred layers, and the contact angles of the droplets with the surface are measured. The critical surface tension is determined from these contact angles by the method of Zisman (W.A. Zisman, Adv. Chem.
Ser., 43 (1964), 1-51 and Phys. Chem. Surfaces, A.W. Adamson, New York 1982). The following values are found. -Polymer from ExampleCrit. surface tension [mN~m]
3 21.7 4 23.8 25.2 6 25.2 (For comparison: A polyethylene surface gives a value of 31 mN/m in this measurement).
' ~
Claims (12)
1. An amphiphilic copolymer containing silanyl groups and structural units derived from at least one monomer of the formula I
(I) and at least one monomer of the formula II
(II) in which A- is CH3- or CF3-, -B- is -CH2- or -CF2-, n is an integer from 5 to 25, m is an integer from zero to 12, X- is -O-, -NR1- or -Z-, in which R1- is H-, CH3-(CH2)n- or CF3-(CF2)n-(CH2)m--Z- is -X'-(CH2)n-X' or , p is an integer from 2 to 10, 1 is an integer from 1 to 10 and -X'- is -O- or -NR1-, -Y is -H, -CH3, -CN, -Cl, -Br or -F, -D is -SiR2(SiR23)2, -Si(SiR23)3, -SiR22-SiR23 or -(SiR22)2-SiR23, in which R2 is C1-C3-alkyl, -E- is C1-C4-alkylene and -L- is or
(I) and at least one monomer of the formula II
(II) in which A- is CH3- or CF3-, -B- is -CH2- or -CF2-, n is an integer from 5 to 25, m is an integer from zero to 12, X- is -O-, -NR1- or -Z-, in which R1- is H-, CH3-(CH2)n- or CF3-(CF2)n-(CH2)m--Z- is -X'-(CH2)n-X' or , p is an integer from 2 to 10, 1 is an integer from 1 to 10 and -X'- is -O- or -NR1-, -Y is -H, -CH3, -CN, -Cl, -Br or -F, -D is -SiR2(SiR23)2, -Si(SiR23)3, -SiR22-SiR23 or -(SiR22)2-SiR23, in which R2 is C1-C3-alkyl, -E- is C1-C4-alkylene and -L- is or
2. A copolymer as claimed in claim 1, wherein -X- is -O-, -NH- or -Z-, -X'- is -O- or -NH-, -D is -(SiR22)-SiR33, R2 is methyl, -E- is C2-alkylene, -L-is -NH- or and -Y is -H or -CH3.
3. A copolymer as claimed in claim 1, wherein the proportion of structural units derived from silanyl-containing monomers of the formula II is 5 to 98 %
by weight and the proportion of structural units derived from monomers of the formula I is 95 to 2 %
by weight, the proportions of the structural units adding up to a total of 100 % by weight.
by weight and the proportion of structural units derived from monomers of the formula I is 95 to 2 %
by weight, the proportions of the structural units adding up to a total of 100 % by weight.
4. A copolymer as claimed in claim 3, wherein the proportion of structural units derived from silanyl-containing monomers of the formula II is 30 to 85 %
by weight and the proportion of structural units derived from monomers of the formula I is 70 to 15 %
by weight.
by weight and the proportion of structural units derived from monomers of the formula I is 70 to 15 %
by weight.
5. A copolymer as claimed in claim 1, comprising struc-tural units derived from at least one monomer each of the formula I and II and at least one further functional comonomer.
6. A copolymer as claimed in claim 5, wherein the structural units derived from a further functional comonomer carry radiation-crosslinkable units.
7. A copolymer as claimed in claim 5, wherein the proportions of structural units derived from monomers of the formula I is 90 to 5 % by weight, the proportions of structural units derived from monomers of the formula II is 5 to 90 % by weight and the proportions of structural units derived from further functional comonomers is 5 to 60 % by weight, the proportions of the structural units adding up to 100 % by weight.
8. A copolymer as claimed in claim 7, wherein the proportions of structural units derived from monomers of the formula I is 60 to 20 % by weight, the proportions of structural units derived from monomers of the formula II is 20 to 60 % by weight and the proportion of structural units derived from further functional comonomers is 20 to 40 % by weight.
9. A layer element comprising a film applied to a carrier, which is composed of at least one monomolecular layer containing a copolymer as claimed in claim 1 or 5.
10. A process for the preparation of a layer element as claimed in claim 9, which comprises dissolving at least one copolymer as claimed in claim 1 or 5 in a volatile organic, water-immiscible solvent, spreading the solution at the water/air interface, compressing the layer formed after evaporation of the solvent and transferring it to a solid support by the Langmuir-Blodgett method.
11. Use of the layer element as claimed in claim 9 for optical purposes.
12. Use of a layer element comprising a film applied to a support, which is composed of at least one monomolecular layer containing a copolymer as claimed in claim 6, for lithographic purposes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4108359 | 1991-03-15 | ||
| DEP4108359.8 | 1991-03-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2061325A1 true CA2061325A1 (en) | 1992-09-16 |
Family
ID=6427325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002061325A Abandoned CA2061325A1 (en) | 1991-03-15 | 1992-03-13 | Amphiphilic polymers containing silane units and film comprising at least one monomolecular layer produced therefrom |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5256749A (en) |
| EP (1) | EP0503420A1 (en) |
| JP (1) | JPH0570526A (en) |
| KR (1) | KR920018114A (en) |
| CA (1) | CA2061325A1 (en) |
| FI (1) | FI921076A (en) |
| IE (1) | IE920827A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2729942B1 (en) * | 1995-01-30 | 1997-04-18 | Rhone Poulenc Chimie | PROCESS FOR THE TREATMENT OF A GLASS TO REDUCE ITS WETABILITY BY GALLIUM AND APPARATUS MADE FROM A GLASS THUS PROCESSED |
| EP0781777A1 (en) * | 1995-12-28 | 1997-07-02 | Menicon Co., Ltd. | Silicon-containing compound and ocular lens material |
| US6207578B1 (en) | 1999-02-19 | 2001-03-27 | Micron Technology, Inc. | Methods of forming patterned constructions, methods of patterning semiconductive substrates, and methods of forming field emission displays |
| AU2001264623A1 (en) * | 2000-05-16 | 2001-11-26 | Biocure, Inc. | Membranes formed from amphiphilic copolymers |
| US20160280807A1 (en) * | 2015-03-24 | 2016-09-29 | Mark D. Soucek | Preparation of non-isocyanate urethane (meth) acrylates for urethane functional latex |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2117669A (en) * | 1982-03-05 | 1983-10-19 | Nat Res Dev | Polymeric films |
| JPH0699517B2 (en) * | 1987-02-06 | 1994-12-07 | 株式会社メニコン | Soft contact lens material |
| KR910005881B1 (en) * | 1987-05-21 | 1991-08-06 | 휴우즈 에어크라프트 캄파니 | Silicon-containing negative resist material and process for its use in patterning substrates |
| DE3811241A1 (en) * | 1988-04-02 | 1989-10-12 | Hoechst Ag | SILYLATING REAGENTS FOR THE PRODUCTION OF BINDERS CONTAINING SILANYL GROUPS IN THE SIDE CHAIN, SOLUBLE IN AQUEOUS ALKALI |
-
1992
- 1992-03-02 EP EP92103535A patent/EP0503420A1/en not_active Withdrawn
- 1992-03-12 FI FI921076A patent/FI921076A/en unknown
- 1992-03-13 US US07/850,581 patent/US5256749A/en not_active Expired - Fee Related
- 1992-03-13 CA CA002061325A patent/CA2061325A1/en not_active Abandoned
- 1992-03-13 JP JP4055471A patent/JPH0570526A/en active Pending
- 1992-03-13 IE IE082792A patent/IE920827A1/en unknown
- 1992-03-14 KR KR1019920004189A patent/KR920018114A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FI921076A (en) | 1992-09-16 |
| JPH0570526A (en) | 1993-03-23 |
| EP0503420A1 (en) | 1992-09-16 |
| KR920018114A (en) | 1992-10-21 |
| IE920827A1 (en) | 1992-09-23 |
| US5256749A (en) | 1993-10-26 |
| FI921076A0 (en) | 1992-03-12 |
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