CA1049682A - Carboxyfunctional silicone containing thermoplastics - Google Patents
Carboxyfunctional silicone containing thermoplasticsInfo
- Publication number
- CA1049682A CA1049682A CA218,436A CA218436A CA1049682A CA 1049682 A CA1049682 A CA 1049682A CA 218436 A CA218436 A CA 218436A CA 1049682 A CA1049682 A CA 1049682A
- Authority
- CA
- Canada
- Prior art keywords
- average value
- radical
- percent
- units
- siloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Abstract
ABSTRACT OF THE DISCLOSURE
Carboxyfunctional silicone containing thermo-plastics are disclosed which have enhanced properties, such as lubricity, internal release and wear resistance, as compared to the thermoplastics per se. These improved thermoplastics are useful inter alia in bearings, tape cartridges and cassettes, phonograph records, toys and containers.
Carboxyfunctional silicone containing thermo-plastics are disclosed which have enhanced properties, such as lubricity, internal release and wear resistance, as compared to the thermoplastics per se. These improved thermoplastics are useful inter alia in bearings, tape cartridges and cassettes, phonograph records, toys and containers.
Description
~0~i8~
A thermoplastic material is any material which softens or -fuses upon heating and hardens or becomes rigid again when cooled. Thermoplastics -find a wide variety of uses such as in bearings, tape cartridges and cassettes, phonograph records, toys and containers.
The term "thermoplastic" as used herein is used in the broadest sense as used by those skilled in the art to mean not only the thermoplastic material per se but to also include thermoplastic compositions as they are more commonly used containing modifiers such as plasticizers, fillers, dyes and pigments, stabilizers and the like. Examples of thermoplastic materials useful in the present invention are the polyvinyl halides, polyamides, fluorocarbons, polyolefins, polystyrenes, polyurethanes, cellulosic resins, acrylic resins~
polyolefin sulfides, phenolic resins, polycarbonates, polysulfones, acetals, polyimides, polyxylylenes, polyoxyalkylenes and polyarylene oxides, as well as copolymers of such materials such as the acrylonitrile- ;
butadiene-styrene ~ABS), styrene-acrylonitrile (SAN), or styrene-acrylonitrile-silicone (SANS) copolymers.
The present invention is based upon the discovery that the incorporation o-f a carboxyfunctional siloxane into a thermoplastic material enhances the properties or characteristics thereof in one or more ways. Stated another way, a composition consisting essentially of 90 to 99.9 percent by weight of a thermoplastic material and 0.1 to 10 percent by weight of a carboxyfunctional siloxane has been found to have enhanced properties or characteristics when compared to the thermoplastic ,,~ ..j ....
ater1al per se.
By way of illustration of-the enhanced properties obtained in accordance with this invention, articles or products having self-lubricating properties can be made in accordance ~lith these teachings. Also, products or articles having increased resistance to wear can be produced. Further, thermoplastics containing carboxy-functional siloxanes as taught herein are more easily, efficiently, and economically processed, e.g., less friction during transfer, injection or extrusion molding is generally observed resulting in faster molding times and fewer defective parts. Also, better release of parts from the molds is obtained again resulting in fewer defective parts as well as longer mold life with minimal down time for cleaning and repair.
While the amount of carboxyfunctional siloxane incorporated into the thermoplastic material can range from 0.1 to 10 percent by weightg generally an amount in the range of 0.25 to 5 percent by weight is preferred as most satisfactory and economical results can be achieved at this level of usage.
The carboxyfunctional siloxane can be mixed into the thermoplastic material by any known means and/or mixing devices, and at any time. ~hat is, at this time there is no known criticality with regard to this aspect of the practice of this invention. ~or optimum results it is obviously desirable that the carboxy-functional siloxane be uniformly dispersed throughout the thermoplastic.
~0 The carboxyfunctional siloxanes useful in ~hlS invention ~re composed of from 0.1 to 50 mole percent RaR'bSiO4 a -~ units and ~Iom 50 to 9~.9 mole percent of R''cSiO4 c units wherein R is a carboxy-functional radical, a has an average value o~ from 1 to 3, R' is a hydrocarbon or halogenated hydrocarbon radical, b has an average value from O to ~, the sum of a + b is from 1 to 3, R" is a hydrocarbon or halogenated hydrocarbon radical, and c has an average value of from O to 3~
In the above formula R can be any carboxyfunctional radicalO In its broadest meaning herein a carboxy-functional radical is ore which contains a COOH group and is attached to the silico~ atom via a silicon-carbon (Si-C) bond. So far as is known at this time, these two characteristics are the only essential ones for the instant invention. A preferred embodiment o~
R is when it is a carboxyfunctional radical of the structure HOOC-Q- wherein Q is a divalent linking group attached to the silicon atom via a sil;con-to-carbon bondO Preferred embodiments of Q are alkylene radicals containing from to 10 carbon atoms, and radicals containing from 2 to 10 carbon atoms whish are composed of carbon, hydrogen and sulfur atoms, the sulfur atoms being present in the form of thioether linkages. Ill~strative examples of Q are in^orporated in the disclosure and examples `~
whi^h follow. Specific examples of suitable R radical~
include, for example, -CH2CH2COOH, -CH2CH(CH3)COOH, -(CH2)6COOH, -(CH2)11COOH, -(CH2)1~COOH, -CH2CH2SCH2COOH, 9tj~
-C~ -C~z-C~ CC)C~ C~12-C~ .;-C~ -C~1zCO0~ C~12C~20Cf~2C00~, "
-C~14~S-C~H4-C00~1, -C~12C~(CH3)C0-C~2CH2COOHJ and -~C~I2)3CS-C~2C~12C00~1. It is pref`erable that the R
radical contain no more than 18 carbon a~Joms. I'here can be l, 2 or 3 R radicals attached to the silicon atoms, i.e., a has an average value of from l to 3.
Generally speaking there will be only one R radical (a=l) attached to most silicon atoms since these are the most practical siloxanes to prepare at this time.
The R' radical can be any hydrocarbon or halo-genated hydrocarbon radical which is compatible with the carboxyfunctional radical. By way of illustration, R' can be an alkyl radical such as the methyl, ethyl, propyl, butyl, octyl, dodecyl, octadecyl and myricyl radicals; an alkenyl radical such as the vinyl, allyl and hexenyl radicals; cycloalkyl radicals such as the cyclobutyl and cyclohexyl radicals; aryl radicals such as the phenyl, xenyl and naphthyl radicals; aralkyl radicals such as the benzyl and 2-phenylethyl radicals;
alkaryl radicals such as the tolyl, xyIyl and mesityl radicals; and the corresponding halohydrocarbon radicals such as the 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoro-propyl, chlorocyclohexyl, bromphenyl? chlorophenyl, alpha, alpha, alpha-trifluorotolyl and the dichloroxenyl radicals. It is preferred that R' contain from l to 18 carbon atoms with the methyl radical being most preferred.
There can be 0, l or 2 R' radicals attached to each silicon atom, io e., the average value of b is f`rom 0 `~ 2, so lor.g as ~he sum of` a + b (the total of R and R' radicals attached to each silicon atom) does not exceed 3 ~l.e., the sum of a + b is from 1 to 3). Preferably b has a value of 0 or 1.
Thè R" radical in the above formula can be any hydrocarbon or halogenated hydrocarbon radical.
For specific examples of` R" radicals reference is ma~e to the examples for R' set forth above which are equally applicable here and nct listed again for the sake of brevity. The subscript c can have an average value of from 0 to 3, i.e., c can be 0, 1, 2 or 3. Preferably c has an average value of 2.
The siloxanes of this invention can be composed of from 0.1 to 50 mole percent of the carboxyfunctional siloxane units and from 50 to 99.9 mole percent of the other siloxane units. ~hile it is obvious from the foregoïng that the siloxane can be composed of up to 50 mole percent carbuxyrutlctiorl~i siloxane units, it is preferred at this time that the carboxyfunctional siloxane units constitute from 0.~5 to 10 mole percent of the total siloxane units present.
Now in order that those skilled in the art may better understand how the present invention can be practiced, the following examples are given by way of illustration and not by way of limitation. All parts and percents are by weight and all viscosities measured at 25C. unless otherwise specified.
Example 1 To measure the ability of the carboxyfunctional siloxanes of this invention to enhance the lubricity ~nd release charclctrristlcs o~` thermoplastics, vary~ng amounts of the carbo~yfunction~l slloxanes Ldentified below were incorporated into polystyrene. This poly-styrene was then used to make a closure (bottle cap) by compression moldi~g in a two part mold. During the molding process the male part of the mokl, which has standard threads, shapes the inside of the closure.
These threads prevent the closure from being removed straight from the mold. Instead it must be unscrewed.
This is accomplished by removing the female part of the closure mold and replacing it with another female mold which is connected to a torque wrenchO This wrench has been set up to measure the amount of torque required to unscrew the closure from the male part of the mold.
The initial or break-away torque is recorded. The lower the torque required, the better or more efficient the carboxyfunctional siloxane is performing. The "mean"
torque values reported i n the table below constitute an average of approximately fifteen experiments.
The carboxyfunctional siloxanes employed were as follows: -(A) A trimethylsilyl endblocked siloxane composed of about 99 mole percent (CH3)2SiO units and about 1 mole percent (CH3)HOOCCH2SCH2CH2SiO units, and having a viscosity of about 23,000 cs.
(B) A trimethylsilyl endblocked siloxane composed of about 99 mole percent (CH3)2SiO units and about 1 mole percent (CH3)HOOCCH2SCH2CH2SiO units, and having a viscosity of about 350 cs.
(C) A trimethylsilyl endblocked siloxane composed of about 9~ o:L.e percenl; (C~l~)2SiO urlits and about 6 mole percent (C'I3)HOOCCH2SC~2CH2S10 units, and ~.a~ing a vlscosi-ty of about 900 cs.
(D) A trimethylsilyl endb].oc~ed siloxane composed of about 90 mole percent (CH3)2SiO units and about lO mole percent (CE~3)HOOCC'~2SC'n2CH~SiO
unlts, and having a viscosity of about 1135 cs.
The siloxane admixed with the polystyrene and the amount thereof as well as the test results are set forth in ~he table below.
Siloxane Weight ~ Mean Torque (in-lb) None* None 86 o 9 A 0.1 6i5o6 A 0025 50.9 A 0.5 45~3 A 1.0 34>3 B 0Oo5 8705 B Ool 84~9 B 0025 62q3 C Ool 104~9 C 0025 69~9 D Ool 11401 :~) ' 0.25 80 ~ 1 : *Control included for comparison--polystyrene per se
A thermoplastic material is any material which softens or -fuses upon heating and hardens or becomes rigid again when cooled. Thermoplastics -find a wide variety of uses such as in bearings, tape cartridges and cassettes, phonograph records, toys and containers.
The term "thermoplastic" as used herein is used in the broadest sense as used by those skilled in the art to mean not only the thermoplastic material per se but to also include thermoplastic compositions as they are more commonly used containing modifiers such as plasticizers, fillers, dyes and pigments, stabilizers and the like. Examples of thermoplastic materials useful in the present invention are the polyvinyl halides, polyamides, fluorocarbons, polyolefins, polystyrenes, polyurethanes, cellulosic resins, acrylic resins~
polyolefin sulfides, phenolic resins, polycarbonates, polysulfones, acetals, polyimides, polyxylylenes, polyoxyalkylenes and polyarylene oxides, as well as copolymers of such materials such as the acrylonitrile- ;
butadiene-styrene ~ABS), styrene-acrylonitrile (SAN), or styrene-acrylonitrile-silicone (SANS) copolymers.
The present invention is based upon the discovery that the incorporation o-f a carboxyfunctional siloxane into a thermoplastic material enhances the properties or characteristics thereof in one or more ways. Stated another way, a composition consisting essentially of 90 to 99.9 percent by weight of a thermoplastic material and 0.1 to 10 percent by weight of a carboxyfunctional siloxane has been found to have enhanced properties or characteristics when compared to the thermoplastic ,,~ ..j ....
ater1al per se.
By way of illustration of-the enhanced properties obtained in accordance with this invention, articles or products having self-lubricating properties can be made in accordance ~lith these teachings. Also, products or articles having increased resistance to wear can be produced. Further, thermoplastics containing carboxy-functional siloxanes as taught herein are more easily, efficiently, and economically processed, e.g., less friction during transfer, injection or extrusion molding is generally observed resulting in faster molding times and fewer defective parts. Also, better release of parts from the molds is obtained again resulting in fewer defective parts as well as longer mold life with minimal down time for cleaning and repair.
While the amount of carboxyfunctional siloxane incorporated into the thermoplastic material can range from 0.1 to 10 percent by weightg generally an amount in the range of 0.25 to 5 percent by weight is preferred as most satisfactory and economical results can be achieved at this level of usage.
The carboxyfunctional siloxane can be mixed into the thermoplastic material by any known means and/or mixing devices, and at any time. ~hat is, at this time there is no known criticality with regard to this aspect of the practice of this invention. ~or optimum results it is obviously desirable that the carboxy-functional siloxane be uniformly dispersed throughout the thermoplastic.
~0 The carboxyfunctional siloxanes useful in ~hlS invention ~re composed of from 0.1 to 50 mole percent RaR'bSiO4 a -~ units and ~Iom 50 to 9~.9 mole percent of R''cSiO4 c units wherein R is a carboxy-functional radical, a has an average value o~ from 1 to 3, R' is a hydrocarbon or halogenated hydrocarbon radical, b has an average value from O to ~, the sum of a + b is from 1 to 3, R" is a hydrocarbon or halogenated hydrocarbon radical, and c has an average value of from O to 3~
In the above formula R can be any carboxyfunctional radicalO In its broadest meaning herein a carboxy-functional radical is ore which contains a COOH group and is attached to the silico~ atom via a silicon-carbon (Si-C) bond. So far as is known at this time, these two characteristics are the only essential ones for the instant invention. A preferred embodiment o~
R is when it is a carboxyfunctional radical of the structure HOOC-Q- wherein Q is a divalent linking group attached to the silicon atom via a sil;con-to-carbon bondO Preferred embodiments of Q are alkylene radicals containing from to 10 carbon atoms, and radicals containing from 2 to 10 carbon atoms whish are composed of carbon, hydrogen and sulfur atoms, the sulfur atoms being present in the form of thioether linkages. Ill~strative examples of Q are in^orporated in the disclosure and examples `~
whi^h follow. Specific examples of suitable R radical~
include, for example, -CH2CH2COOH, -CH2CH(CH3)COOH, -(CH2)6COOH, -(CH2)11COOH, -(CH2)1~COOH, -CH2CH2SCH2COOH, 9tj~
-C~ -C~z-C~ CC)C~ C~12-C~ .;-C~ -C~1zCO0~ C~12C~20Cf~2C00~, "
-C~14~S-C~H4-C00~1, -C~12C~(CH3)C0-C~2CH2COOHJ and -~C~I2)3CS-C~2C~12C00~1. It is pref`erable that the R
radical contain no more than 18 carbon a~Joms. I'here can be l, 2 or 3 R radicals attached to the silicon atoms, i.e., a has an average value of from l to 3.
Generally speaking there will be only one R radical (a=l) attached to most silicon atoms since these are the most practical siloxanes to prepare at this time.
The R' radical can be any hydrocarbon or halo-genated hydrocarbon radical which is compatible with the carboxyfunctional radical. By way of illustration, R' can be an alkyl radical such as the methyl, ethyl, propyl, butyl, octyl, dodecyl, octadecyl and myricyl radicals; an alkenyl radical such as the vinyl, allyl and hexenyl radicals; cycloalkyl radicals such as the cyclobutyl and cyclohexyl radicals; aryl radicals such as the phenyl, xenyl and naphthyl radicals; aralkyl radicals such as the benzyl and 2-phenylethyl radicals;
alkaryl radicals such as the tolyl, xyIyl and mesityl radicals; and the corresponding halohydrocarbon radicals such as the 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoro-propyl, chlorocyclohexyl, bromphenyl? chlorophenyl, alpha, alpha, alpha-trifluorotolyl and the dichloroxenyl radicals. It is preferred that R' contain from l to 18 carbon atoms with the methyl radical being most preferred.
There can be 0, l or 2 R' radicals attached to each silicon atom, io e., the average value of b is f`rom 0 `~ 2, so lor.g as ~he sum of` a + b (the total of R and R' radicals attached to each silicon atom) does not exceed 3 ~l.e., the sum of a + b is from 1 to 3). Preferably b has a value of 0 or 1.
Thè R" radical in the above formula can be any hydrocarbon or halogenated hydrocarbon radical.
For specific examples of` R" radicals reference is ma~e to the examples for R' set forth above which are equally applicable here and nct listed again for the sake of brevity. The subscript c can have an average value of from 0 to 3, i.e., c can be 0, 1, 2 or 3. Preferably c has an average value of 2.
The siloxanes of this invention can be composed of from 0.1 to 50 mole percent of the carboxyfunctional siloxane units and from 50 to 99.9 mole percent of the other siloxane units. ~hile it is obvious from the foregoïng that the siloxane can be composed of up to 50 mole percent carbuxyrutlctiorl~i siloxane units, it is preferred at this time that the carboxyfunctional siloxane units constitute from 0.~5 to 10 mole percent of the total siloxane units present.
Now in order that those skilled in the art may better understand how the present invention can be practiced, the following examples are given by way of illustration and not by way of limitation. All parts and percents are by weight and all viscosities measured at 25C. unless otherwise specified.
Example 1 To measure the ability of the carboxyfunctional siloxanes of this invention to enhance the lubricity ~nd release charclctrristlcs o~` thermoplastics, vary~ng amounts of the carbo~yfunction~l slloxanes Ldentified below were incorporated into polystyrene. This poly-styrene was then used to make a closure (bottle cap) by compression moldi~g in a two part mold. During the molding process the male part of the mokl, which has standard threads, shapes the inside of the closure.
These threads prevent the closure from being removed straight from the mold. Instead it must be unscrewed.
This is accomplished by removing the female part of the closure mold and replacing it with another female mold which is connected to a torque wrenchO This wrench has been set up to measure the amount of torque required to unscrew the closure from the male part of the mold.
The initial or break-away torque is recorded. The lower the torque required, the better or more efficient the carboxyfunctional siloxane is performing. The "mean"
torque values reported i n the table below constitute an average of approximately fifteen experiments.
The carboxyfunctional siloxanes employed were as follows: -(A) A trimethylsilyl endblocked siloxane composed of about 99 mole percent (CH3)2SiO units and about 1 mole percent (CH3)HOOCCH2SCH2CH2SiO units, and having a viscosity of about 23,000 cs.
(B) A trimethylsilyl endblocked siloxane composed of about 99 mole percent (CH3)2SiO units and about 1 mole percent (CH3)HOOCCH2SCH2CH2SiO units, and having a viscosity of about 350 cs.
(C) A trimethylsilyl endblocked siloxane composed of about 9~ o:L.e percenl; (C~l~)2SiO urlits and about 6 mole percent (C'I3)HOOCCH2SC~2CH2S10 units, and ~.a~ing a vlscosi-ty of about 900 cs.
(D) A trimethylsilyl endb].oc~ed siloxane composed of about 90 mole percent (CH3)2SiO units and about lO mole percent (CE~3)HOOCC'~2SC'n2CH~SiO
unlts, and having a viscosity of about 1135 cs.
The siloxane admixed with the polystyrene and the amount thereof as well as the test results are set forth in ~he table below.
Siloxane Weight ~ Mean Torque (in-lb) None* None 86 o 9 A 0.1 6i5o6 A 0025 50.9 A 0.5 45~3 A 1.0 34>3 B 0Oo5 8705 B Ool 84~9 B 0025 62q3 C Ool 104~9 C 0025 69~9 D Ool 11401 :~) ' 0.25 80 ~ 1 : *Control included for comparison--polystyrene per se
Claims (5)
1. A composition consisting essentially of (A) from 90 to 99.9 percent by weight of a polymeric thermo-plastic material and (B) from 0.1 to 10 percent by weight of a carboxyfunctional siloxane composed of from 0.1 to 50 mole percent of units and from 50 to 99.9 mole percent of units wherein R is a carboxyfunctional radical which contains a -COOH group and is attached to the silicon atom via a silicon-carbon bond, a has an average value from 1 to 3, R' is a hydrocarbon or halogenated hydrocarbon radical, b has an average value from 0 to 2, the sum of a + b is from 1 to 3, R" is a hydrocarbon or halogenated hydrocarbon radical, and c has an average value from 0 to 3.
2. A composition as defined in claim 1 wherein (A) is from 95 to 99.75 percent 9 (B) is from 0.25 to 5 percent and is composed of 0.25 to 10 mole percent units and 95 to 99.75 mole percent units, R is a radical of the structure HOOC-Q-wherein Q is a divalent linking group attached to the silicon atom via a silicon to carbon bond, I has an average value of 1, R' is a hydrocarbon radical containing from 1 to 18 carbon atoms, b has an average value of 0 to 1, and R" is a hydrocarbon radical containing from 1 to 18 carbon atoms.
3. A composition as defined in claim 2 wherein in the siloxane Q is an alkylene radical containing from 2 to 10 carbon atoms, R' is a methyl radical, b has an average value of 1, R" is a methyl radical, and c has an average value of 2.
4. A composition as defined in claim 2 wherein in the siloxane Q is composed of carbon, hydrogen and sulfur atoms, the sulfur atoms being present in the form of thioether linkages, said Q containing from 2 to 10 carbon atoms, R' is a methyl radical, b has an average value of 1, R" is a methyl radical, and c has an average value of 2.
5. A composition as defined in claim 1 wherein the thermoplastic material is selected from the group consisting of polystyrene, polyvinyl chloride, nylon, polytetrafluoroethylene, polypropylene, poly-carbonate, acrylonitrile-butadiene-styrene terpolymers, and styrene-acrylonitrile copolymers.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47774074A | 1974-06-10 | 1974-06-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049682A true CA1049682A (en) | 1979-02-27 |
Family
ID=23897162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA218,436A Expired CA1049682A (en) | 1974-06-10 | 1975-01-22 | Carboxyfunctional silicone containing thermoplastics |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5344178B2 (en) |
| AT (1) | AT343361B (en) |
| CA (1) | CA1049682A (en) |
| FR (1) | FR2273849A1 (en) |
| GB (1) | GB1460128A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857251A (en) * | 1988-04-14 | 1989-08-15 | Kimberly-Clark Corporation | Method of forming a nonwoven web from a surface-segregatable thermoplastic composition |
| US4923914A (en) * | 1988-04-14 | 1990-05-08 | Kimberly-Clark Corporation | Surface-segregatable, melt-extrudable thermoplastic composition |
| US4976788A (en) * | 1988-06-03 | 1990-12-11 | Kimberly-Clark Corporation | Method of cleaning melt-processing equipment with a thermoplastic polyolefin and a bifunctional siloxane |
| US5085920A (en) * | 1990-04-30 | 1992-02-04 | Kimberly-Clark Corporation | Nonwoven wipe having improved grease release |
| US5114646A (en) * | 1989-09-18 | 1992-05-19 | Kimberly-Clark Corporation | Method of increasing the delay period of nonwoven webs having delayed wettability |
| US5120888A (en) * | 1988-04-14 | 1992-06-09 | Kimberly-Clark Corporation | Surface-segregatable, melt-extrudable thermoplastic composition |
| US5145727A (en) * | 1990-11-26 | 1992-09-08 | Kimberly-Clark Corporation | Multilayer nonwoven composite structure |
| US5149576A (en) * | 1990-11-26 | 1992-09-22 | Kimberly-Clark Corporation | Multilayer nonwoven laminiferous structure |
| US5225263A (en) * | 1990-02-08 | 1993-07-06 | Frudenberg Spunweb S.A. Societe Anonyme A. Directoire | Nonwovens of synthetic continuous filaments including at least a part with modified surface properties, process for their manufacture and their applications |
| US5344862A (en) * | 1991-10-25 | 1994-09-06 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
| US5356585A (en) * | 1993-07-01 | 1994-10-18 | Dow Corning Corporation | Process of extruding snythetic thermoplastic resins using organosilicon resinous compositions as extrusion lubricants |
| US5494855A (en) * | 1994-04-06 | 1996-02-27 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
| US5641822A (en) * | 1989-09-18 | 1997-06-24 | Kimberly-Clark Corporation | Surface-segregatable compositions and nonwoven webs prepared therefrom |
| US5656361A (en) * | 1996-07-23 | 1997-08-12 | Kimberly-Clark Worldwide, Inc. | Multiple application meltblown nonwoven wet wipe and method |
| US5696191A (en) * | 1989-09-18 | 1997-12-09 | Kimberly-Clark Worldwide, Inc. | Surface-segregatable compositions and nonwoven webs prepared therefrom |
| US5708084A (en) * | 1996-08-28 | 1998-01-13 | Dow Corning Corporation | Organic polymers modified with silicone materials |
| US5708085A (en) * | 1996-08-28 | 1998-01-13 | Dow Corning Corporation | Low density polyethylene modified with silicone materials |
| US5789473A (en) * | 1995-01-17 | 1998-08-04 | Dow Corning Corporation | Polyolefin composition containing diorganopolysiloxane process aid |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6052326B2 (en) * | 1979-10-05 | 1985-11-19 | 日本ケ−ブル・システム株式会社 | control cable |
| JPS6050386B2 (en) * | 1980-07-31 | 1985-11-08 | ト−レ・シリコ−ン株式会社 | Vinyl resin composition |
| US4535113A (en) * | 1984-03-13 | 1985-08-13 | Union Carbide Corporation | Olefin polymer compositions containing silicone additives and the use thereof in the production of film material |
| US4994532A (en) * | 1989-06-16 | 1991-02-19 | General Electric Company | Polycarbonate-silicone block copolymer compositions |
| JP2008523209A (en) | 2004-12-07 | 2008-07-03 | ダウ グローバル テクノロジーズ インコーポレイティド | Polymers containing fluoropolymer processing aids and catalyst neutralizers |
| US20080132654A1 (en) * | 2004-12-07 | 2008-06-05 | Dow Global Technologies Inc. | Polymer Containing Polysiloxane Processing Aid and Catalyst Neutralizer |
| ES2606401T3 (en) | 2008-12-17 | 2017-03-23 | 3M Innovative Properties Company | Thermoplastic silicone based polymer processing additives for injection molding applications |
| CN102300935B (en) | 2008-12-17 | 2014-03-19 | 3M创新有限公司 | Silicone polyoxamide process additives for high clarity applications |
| KR20150021101A (en) | 2012-06-11 | 2015-02-27 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Melt-processable compositions having silicone-containing polymeric process additive and synergist |
| GB2509128A (en) * | 2012-12-20 | 2014-06-25 | Dow Corning | Process for improving fire resistance of an organic polymer |
-
1975
- 1975-01-22 CA CA218,436A patent/CA1049682A/en not_active Expired
- 1975-02-21 AT AT131475A patent/AT343361B/en not_active IP Right Cessation
- 1975-03-19 JP JP3349075A patent/JPS5344178B2/ja not_active Expired
- 1975-05-21 GB GB2177775A patent/GB1460128A/en not_active Expired
- 1975-06-06 FR FR7517733A patent/FR2273849A1/en active Granted
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857251A (en) * | 1988-04-14 | 1989-08-15 | Kimberly-Clark Corporation | Method of forming a nonwoven web from a surface-segregatable thermoplastic composition |
| US4923914A (en) * | 1988-04-14 | 1990-05-08 | Kimberly-Clark Corporation | Surface-segregatable, melt-extrudable thermoplastic composition |
| US5057262A (en) * | 1988-04-14 | 1991-10-15 | Kimberly-Clark Corporation | Process for melt extruding a surface-segregatable thermoplastic composition |
| US5120888A (en) * | 1988-04-14 | 1992-06-09 | Kimberly-Clark Corporation | Surface-segregatable, melt-extrudable thermoplastic composition |
| US4976788A (en) * | 1988-06-03 | 1990-12-11 | Kimberly-Clark Corporation | Method of cleaning melt-processing equipment with a thermoplastic polyolefin and a bifunctional siloxane |
| US5114646A (en) * | 1989-09-18 | 1992-05-19 | Kimberly-Clark Corporation | Method of increasing the delay period of nonwoven webs having delayed wettability |
| US5696191A (en) * | 1989-09-18 | 1997-12-09 | Kimberly-Clark Worldwide, Inc. | Surface-segregatable compositions and nonwoven webs prepared therefrom |
| US5641822A (en) * | 1989-09-18 | 1997-06-24 | Kimberly-Clark Corporation | Surface-segregatable compositions and nonwoven webs prepared therefrom |
| US5225263A (en) * | 1990-02-08 | 1993-07-06 | Frudenberg Spunweb S.A. Societe Anonyme A. Directoire | Nonwovens of synthetic continuous filaments including at least a part with modified surface properties, process for their manufacture and their applications |
| US5085920A (en) * | 1990-04-30 | 1992-02-04 | Kimberly-Clark Corporation | Nonwoven wipe having improved grease release |
| US5178932A (en) * | 1990-11-26 | 1993-01-12 | Kimberly-Clark Corporation | Three-layer nonwoven composite structure |
| US5178931A (en) * | 1990-11-26 | 1993-01-12 | Kimberly-Clark Corporation | Three-layer nonwoven laminiferous structure |
| US5149576A (en) * | 1990-11-26 | 1992-09-22 | Kimberly-Clark Corporation | Multilayer nonwoven laminiferous structure |
| US5145727A (en) * | 1990-11-26 | 1992-09-08 | Kimberly-Clark Corporation | Multilayer nonwoven composite structure |
| US5344862A (en) * | 1991-10-25 | 1994-09-06 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
| US5413655A (en) * | 1991-10-25 | 1995-05-09 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
| US5356585A (en) * | 1993-07-01 | 1994-10-18 | Dow Corning Corporation | Process of extruding snythetic thermoplastic resins using organosilicon resinous compositions as extrusion lubricants |
| US5494855A (en) * | 1994-04-06 | 1996-02-27 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
| US5789473A (en) * | 1995-01-17 | 1998-08-04 | Dow Corning Corporation | Polyolefin composition containing diorganopolysiloxane process aid |
| US5656361A (en) * | 1996-07-23 | 1997-08-12 | Kimberly-Clark Worldwide, Inc. | Multiple application meltblown nonwoven wet wipe and method |
| US5708084A (en) * | 1996-08-28 | 1998-01-13 | Dow Corning Corporation | Organic polymers modified with silicone materials |
| US5708085A (en) * | 1996-08-28 | 1998-01-13 | Dow Corning Corporation | Low density polyethylene modified with silicone materials |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2506667B2 (en) | 1976-07-08 |
| ATA131475A (en) | 1977-09-15 |
| JPS5344178B2 (en) | 1978-11-27 |
| FR2273849A1 (en) | 1976-01-02 |
| GB1460128A (en) | 1976-12-31 |
| DE2506667A1 (en) | 1975-12-11 |
| AU7761175A (en) | 1976-07-29 |
| AT343361B (en) | 1978-05-26 |
| FR2273849B1 (en) | 1979-04-27 |
| JPS50156555A (en) | 1975-12-17 |
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