CA2143359A1 - Method for improving erasability of erasable marking compositions - Google Patents
Method for improving erasability of erasable marking compositionsInfo
- Publication number
- CA2143359A1 CA2143359A1 CA002143359A CA2143359A CA2143359A1 CA 2143359 A1 CA2143359 A1 CA 2143359A1 CA 002143359 A CA002143359 A CA 002143359A CA 2143359 A CA2143359 A CA 2143359A CA 2143359 A1 CA2143359 A1 CA 2143359A1
- Authority
- CA
- Canada
- Prior art keywords
- shell
- weight
- comonomer
- beta
- alpha
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
Abstract
A method is disclosed for improving the erasability of erasable marking compositions, while maintaining the opacity of the coating and without producing burnishing, by incorporating into the compositions voided latex particles having a shell polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer;
(2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell.
An improved liquid marking composition is also disclosed.
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer;
(2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell.
An improved liquid marking composition is also disclosed.
Description
21~3359 METHOD FOR IMPROVING ERASABILITY OF ERASABLE MARKING
COMPOSmONS
FIELD OF THE INVENTION
This invention relates to a method for improving the erasability of erasable marking compositions by incorporating into the compositions voided latex particles having a crosslinke.l shell.
BACKGROUND OF THE INVENTION
Chalk used to make markings on blackboards or chalkboards is typically made from calcium carbonate formed into a hard solid stick or cake. When the chalk is used, calcium carbonate is transferred to the blackboard surface. A large amount of calcium carbonate dust is also generated when the markings are made and when the blackboard erasers used to wipe away the markings are cleaned by slapping them together. This dust is more than just a housekeeping n~ Ance, it poses health concerns, especially in a classroom setting, because the inhalation of the dust may cause, inter alia, respiratory problems. In addition,the dust is harmful to electronic equipment, such as computers. Therefore, it isdesirable to produce a marking medium useful on a standard blackboard or chalkboard which does not pose health and safety concerns.
Efforts have been made to produce marking media, such as, for example, liquid marking compositions, which do not generate dust or have other deleterious health effects. There has only been limited success in developing liquid marking compositions because, in the effort to produce a healthier marking medium, performance properties of the compositions have been compromised.
One problem is that the liquid marking compositions do not have the same whiteness or opacity on conventional blackboards as conventional chalk.
Opacifiers have been added to solve this problem. As a result of the addition ofthe opacifying agents, however, many of the compositions lose their "erasability," i.e., they leave a hazy, whitish film on the dark blackboard or chalkboard after the board has been wiped with a conventional blackboard eraser or additionally wiped with water. The formation of this undesirable film is referred to as "ghosting."
- ~43359 Another problem with liquid marking compositions has been burnishing of the blackboard, i.e., a glazing, not associated with any physical abrasion, of the blackboard surface caused by a component of the liquid marking composition, such as soft, low melting point polymers and waxy materials.
SUMMARY OF THE INVENTION
I have discovered a method for improving the erasability of erasable marking compositions, while maintaining the opacity of the coating and .
without producing burnishing, by incorporating into the compositions voided latex particles having a shell polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer; or (2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell.
DETAILED DESCRIPTION OF THE INVENTION
The composition and method of this invention involve incorporating into conventional liquid marking compositions voided latex particles having crosslinked shells. The voided latex particles containing a core and a shell maybe prepared by conventional polymerization techniques such as, sequential emulsion polymerization, including those processes disclosed in U.S. Patents 4,427,836; 4,594,363; 4,677,003 4,920,160; 4,970,241, whose disclosures are incorporated herein by reference, and European Patent Application 0,267,726.
The methods disclosed in the aforementioned patents include a step of swelling the multistaged polymer particles with water or solvent in the wet state. Thus, the polymer particles do not become void the water or solvent inside the particles evaporates. Generally, this does not occur until the coating systems to which the polymer particles are added are allowed to dry. Because the polymer particles useful in the composition and method of this invention have a shell formed from a crosslinking monomer, they are resistant to swelling. Thus, it is ~referdble to polymerize the shell polymer after most of the swelling of the core has occurred, i.e., after the addition of base for an acid-rich core; after the addition of acid for an amine-rich core; and after the addition of solvent for a solvent-swellable core.
The voided latex particles useful in composition and method of this invention are formed from a multistaged polymer particle having a core polymer and a shell polymer, wherein the shell polymer is polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinlcing comonomer; or (2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell.
The balance of the monomers used in the aqueous emulsion polymerization of the shell polymer may be at least 1% by weight one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group and one or more non-ionic ethylenically unsaturated monomer.
"Cros~linking comonomer" as used herein refers to a polyfunctional monomer or mixture of monomers which crosslinks a polymer composition during the initial formation thereof. Subsequent drying or other curing tedhniques are not required. Comonomers of this type are well-known and include monomers wherein the functionality is of substantially equivalent reactivity so that uniform crosslinking occurs. Typically, such comonomers contain at least two addition polymerizable vinylidene groups and are a,~-ethylenically unsaturated monocarboxylic acid esters of polyhydric alcohols containing 2-6 ester groups. Suitable crosslinking comonomers include alkylene glycol diacrylates and dimethacrylates, sudh as for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate propylene glycol diacrylate and triethylene glycol dimethylacrylate; 1,3-glycerol dimethacrylate; 1,1,1-trimethylolpropane dimethacrylate; 1,1,1-trimethylolethane diacrylate; pentaerythritol trimethacrylate; 1,2,6-hexane triacrylate; sorbitol pentamethacrylate; methylenebis-acrylamide, methylene bis-methacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinylacetylene, trivinylbenzene, triallyl cyanurate, divinylacetylene, divinylethane, divinyl sulfide, divinyl ether, divinyl sulfone, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyldimethylsilane, glycerol trivinyl ether, divinyl adipate;
dicyclopentenyl (meth)acrylates; dicyclopentenyloxy (meth)acrylates;
unsaturated esters of glycol monodicyclopentenyl ethers; allyl esters of a,~-unsaturated mono- and dicarboxylic acids having terminal ethylenic unsaturation induding allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl itaconate and the like. Allyl methacrylate is preferred. The term (meth)acrylate, as used herein, refers to both acrylate and methacrylate.
Suitable monoethylenically unsaturated monomers containing at least one carboxylic acid group include acrylic acid and methacrylic acid, acryloxy~lo~ionic acid, (meth)acryloxy~ro~ionic acid, itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate. Acrylic acid and methacrylic acid are preferred.
Suitable non-ionic ethylenically unsaturated monomers include styrene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acryl~mi~le, (Cl-C20) alkyl or (C3-C20) alkenyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate and stearyl (meth)acrylate. As used herein, the term "(meth)acrylic" is intended to serve asa generic expression embracing both acrylic and methacrylic.
The core polymer may be the product of aqueous emulsion polyrnerization of one or more monoethylenically unsaturated monomers contAining at least one carboxylic acid group. The core polymer may be obtained by the emulsion homopolymerization of such a monoethylenically unsaturated monomer con~ining at least one carboxylic acid group or by copolymerization of two or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the monoethylenically unsaturated monomer containing at least one carboxylic acid group is copolymerized with one or more non-ionic (that is, having no ionizable group) ethylenically unsaturated monomers.
The core polymer may also contain from about 0.1% to about 20% by weight, based on the weight of the total monomer weight of the core, preferably about 0.1% to about 3% by weight of polyethylenically unsaturated monomer, such as ethylene glycol di(meth)acrylate, allyl (meth)acrylate, 1,3-butane-diol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane trimethacrylate, or divinylbenzene. Alternatively, the core polymer may contain from about 0.1% to about 60% by weight, based on the weight of the total monomer weight of the core, of butadiene.
21433~9 The voided latex particles useful in the method of this invention are incorporated into the conventional liquid marking composition at a level of from about 5% to about 40%, based on the total weight of the liquid marking composition, and preferably from about 10% to about 25%, based on the total weight of the liquid marking composition.
The composition and method of this invention are useful for improving the erasability of both conventional aqueous-based and solvent-based liquid marking compositions. Conventional aqueous-based liquid marking compositions may contain water, voltaile water-miscible solvents, such as methanol, to increase the rate of drying, soluble dyes, fine pigment particles, dispersants and thickeners. Conventional solvent-based liquid marking compositions may contain solvent, dyes, fine pigment particles, dispersants and thickeners.
The following examples illustrate the operation of the invention. These examples are intPn~1er~ merely to illustrate the invention and are not intended nor should they be in~ leled as limiting the scope of the invention since modifications to the process illustrated are considered to be obvious to one of ordinary skill in the art.
21~3359 EXAMPLE 1. PREPARATION OF LIQUID MARKING
COMPOSlTIONS
Comparative voided latex particles and voided latex particles useful in the composition and method of the invention were prepared by the method described in U.S. Patent 4,427,836. Excess ammonia (1.3 equivalents based on thetotal equivalents of methacrylic acid in the particles) was added to the hot (80-85C) dispersion between the polymerizaton of shell II and shell III to convert the acid-rich core to the ammonium salt causing the core to swell with water.
The final particle sizes averaged 400-550 nm and the solid content of the dispersions ranged from 32-43% by weight. All of the dispersions were diluted with water to 20% solids by weight to give the final liquid marking composition.
Table 1.1: Co~ >o~:Lul.s of the Voided Latex Polymers 1 part core*//9 parts(20BMA/78 MMA/2MAA)(Shell l)//x parts(Shell Il) //y parts(Shell III) ~140 nm,5BA/55MMA/40MAA
Voided Latex ShellII Shellm Particles x , - -- y I "o ~iLu 1 C 22.5 100Sty 22.5 100Sty 2Ç 22.5 100Sty 22.5 60Sty/40DVB-55 3C 22.5 100Sty 22.5 75Sty/25ALMA
4C 22.5 100Sty 22.5 85Sty/15ALMA
90MMA/lOSty 20 75MMA/lOSty/15ALMA
6 4 100Sty 9 40Sty/60DVB-55 Notes: The suffix "C" denotes a ~u~ a~dlive.
Abbreviations MMA methyl methacrylate BMA butyl methacrylate BA butyl acrylate MAA methacrylic acid Sty styrene DVB-55 Dow 55% grade of divi~yll~lzene where most of remainder is ethylvi,lylbenzene ALMA allyl methacrylate EXAMPLE2. PERFORMANCE ~ G
Markers contAining the formulations made in accordance with Example 1 were tested for erasability, burni~hing and opacity by marking on both a slatechalkboard and a composition chalkboard at both one cycle and 50 cycles. One cycle is covering a 1-inch-by-2-inch rectangle on the chalkboard surface and erasing the marking using a conventional chalkboard eraser. Fifty cycles is repeating the process 50 times.
Erasability T~tin$
The erasability of each formulation was judged by how well it could be removed, using a conventional chalkboard eraser, in comparison to the erasability of a similar marking made using conventional calcium carbonate chalk. The results are shown in Table 2.1.
Bnrni~hing Testing The burni~hing of each formulation was judged by how much gl~7ing of the chalkboard surface appeared which was not a result of physical abrasion.
The results are shown in Table 2.1.
Opacity T~
The opacity of each formulation was judged by how well the marking developed solid whiteness when dry. The results are shown in Table 2.1.
Table 2.1: pPrfon~ P Results Formul^~inn ~ e Erasability Bl; .. ;~l.;.. ~. Opacity Voided Latex Polymer lC ghosting -- fail yes--fail good (white) 2C ghosting -- fail yes--fail fair (white) 3C ghosting -- fail yes--fail fair (white) 4C ghosting -- fail yes - fail good (white) good (no ~,l,o~li,.g) no--pass good (blue-white) --pass 6 good(noghosting) no-pass good (white) --pass The results indicate that formulations containing voided latex particles having an shell polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer; or (2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell exhibit good erasability (no ghosting) while mAintAining the opacity of the coating and without producing burnishing.
COMPOSmONS
FIELD OF THE INVENTION
This invention relates to a method for improving the erasability of erasable marking compositions by incorporating into the compositions voided latex particles having a crosslinke.l shell.
BACKGROUND OF THE INVENTION
Chalk used to make markings on blackboards or chalkboards is typically made from calcium carbonate formed into a hard solid stick or cake. When the chalk is used, calcium carbonate is transferred to the blackboard surface. A large amount of calcium carbonate dust is also generated when the markings are made and when the blackboard erasers used to wipe away the markings are cleaned by slapping them together. This dust is more than just a housekeeping n~ Ance, it poses health concerns, especially in a classroom setting, because the inhalation of the dust may cause, inter alia, respiratory problems. In addition,the dust is harmful to electronic equipment, such as computers. Therefore, it isdesirable to produce a marking medium useful on a standard blackboard or chalkboard which does not pose health and safety concerns.
Efforts have been made to produce marking media, such as, for example, liquid marking compositions, which do not generate dust or have other deleterious health effects. There has only been limited success in developing liquid marking compositions because, in the effort to produce a healthier marking medium, performance properties of the compositions have been compromised.
One problem is that the liquid marking compositions do not have the same whiteness or opacity on conventional blackboards as conventional chalk.
Opacifiers have been added to solve this problem. As a result of the addition ofthe opacifying agents, however, many of the compositions lose their "erasability," i.e., they leave a hazy, whitish film on the dark blackboard or chalkboard after the board has been wiped with a conventional blackboard eraser or additionally wiped with water. The formation of this undesirable film is referred to as "ghosting."
- ~43359 Another problem with liquid marking compositions has been burnishing of the blackboard, i.e., a glazing, not associated with any physical abrasion, of the blackboard surface caused by a component of the liquid marking composition, such as soft, low melting point polymers and waxy materials.
SUMMARY OF THE INVENTION
I have discovered a method for improving the erasability of erasable marking compositions, while maintaining the opacity of the coating and .
without producing burnishing, by incorporating into the compositions voided latex particles having a shell polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer; or (2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell.
DETAILED DESCRIPTION OF THE INVENTION
The composition and method of this invention involve incorporating into conventional liquid marking compositions voided latex particles having crosslinked shells. The voided latex particles containing a core and a shell maybe prepared by conventional polymerization techniques such as, sequential emulsion polymerization, including those processes disclosed in U.S. Patents 4,427,836; 4,594,363; 4,677,003 4,920,160; 4,970,241, whose disclosures are incorporated herein by reference, and European Patent Application 0,267,726.
The methods disclosed in the aforementioned patents include a step of swelling the multistaged polymer particles with water or solvent in the wet state. Thus, the polymer particles do not become void the water or solvent inside the particles evaporates. Generally, this does not occur until the coating systems to which the polymer particles are added are allowed to dry. Because the polymer particles useful in the composition and method of this invention have a shell formed from a crosslinking monomer, they are resistant to swelling. Thus, it is ~referdble to polymerize the shell polymer after most of the swelling of the core has occurred, i.e., after the addition of base for an acid-rich core; after the addition of acid for an amine-rich core; and after the addition of solvent for a solvent-swellable core.
The voided latex particles useful in composition and method of this invention are formed from a multistaged polymer particle having a core polymer and a shell polymer, wherein the shell polymer is polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinlcing comonomer; or (2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell.
The balance of the monomers used in the aqueous emulsion polymerization of the shell polymer may be at least 1% by weight one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group and one or more non-ionic ethylenically unsaturated monomer.
"Cros~linking comonomer" as used herein refers to a polyfunctional monomer or mixture of monomers which crosslinks a polymer composition during the initial formation thereof. Subsequent drying or other curing tedhniques are not required. Comonomers of this type are well-known and include monomers wherein the functionality is of substantially equivalent reactivity so that uniform crosslinking occurs. Typically, such comonomers contain at least two addition polymerizable vinylidene groups and are a,~-ethylenically unsaturated monocarboxylic acid esters of polyhydric alcohols containing 2-6 ester groups. Suitable crosslinking comonomers include alkylene glycol diacrylates and dimethacrylates, sudh as for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate propylene glycol diacrylate and triethylene glycol dimethylacrylate; 1,3-glycerol dimethacrylate; 1,1,1-trimethylolpropane dimethacrylate; 1,1,1-trimethylolethane diacrylate; pentaerythritol trimethacrylate; 1,2,6-hexane triacrylate; sorbitol pentamethacrylate; methylenebis-acrylamide, methylene bis-methacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinylacetylene, trivinylbenzene, triallyl cyanurate, divinylacetylene, divinylethane, divinyl sulfide, divinyl ether, divinyl sulfone, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyldimethylsilane, glycerol trivinyl ether, divinyl adipate;
dicyclopentenyl (meth)acrylates; dicyclopentenyloxy (meth)acrylates;
unsaturated esters of glycol monodicyclopentenyl ethers; allyl esters of a,~-unsaturated mono- and dicarboxylic acids having terminal ethylenic unsaturation induding allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl itaconate and the like. Allyl methacrylate is preferred. The term (meth)acrylate, as used herein, refers to both acrylate and methacrylate.
Suitable monoethylenically unsaturated monomers containing at least one carboxylic acid group include acrylic acid and methacrylic acid, acryloxy~lo~ionic acid, (meth)acryloxy~ro~ionic acid, itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate. Acrylic acid and methacrylic acid are preferred.
Suitable non-ionic ethylenically unsaturated monomers include styrene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acryl~mi~le, (Cl-C20) alkyl or (C3-C20) alkenyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate and stearyl (meth)acrylate. As used herein, the term "(meth)acrylic" is intended to serve asa generic expression embracing both acrylic and methacrylic.
The core polymer may be the product of aqueous emulsion polyrnerization of one or more monoethylenically unsaturated monomers contAining at least one carboxylic acid group. The core polymer may be obtained by the emulsion homopolymerization of such a monoethylenically unsaturated monomer con~ining at least one carboxylic acid group or by copolymerization of two or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the monoethylenically unsaturated monomer containing at least one carboxylic acid group is copolymerized with one or more non-ionic (that is, having no ionizable group) ethylenically unsaturated monomers.
The core polymer may also contain from about 0.1% to about 20% by weight, based on the weight of the total monomer weight of the core, preferably about 0.1% to about 3% by weight of polyethylenically unsaturated monomer, such as ethylene glycol di(meth)acrylate, allyl (meth)acrylate, 1,3-butane-diol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane trimethacrylate, or divinylbenzene. Alternatively, the core polymer may contain from about 0.1% to about 60% by weight, based on the weight of the total monomer weight of the core, of butadiene.
21433~9 The voided latex particles useful in the method of this invention are incorporated into the conventional liquid marking composition at a level of from about 5% to about 40%, based on the total weight of the liquid marking composition, and preferably from about 10% to about 25%, based on the total weight of the liquid marking composition.
The composition and method of this invention are useful for improving the erasability of both conventional aqueous-based and solvent-based liquid marking compositions. Conventional aqueous-based liquid marking compositions may contain water, voltaile water-miscible solvents, such as methanol, to increase the rate of drying, soluble dyes, fine pigment particles, dispersants and thickeners. Conventional solvent-based liquid marking compositions may contain solvent, dyes, fine pigment particles, dispersants and thickeners.
The following examples illustrate the operation of the invention. These examples are intPn~1er~ merely to illustrate the invention and are not intended nor should they be in~ leled as limiting the scope of the invention since modifications to the process illustrated are considered to be obvious to one of ordinary skill in the art.
21~3359 EXAMPLE 1. PREPARATION OF LIQUID MARKING
COMPOSlTIONS
Comparative voided latex particles and voided latex particles useful in the composition and method of the invention were prepared by the method described in U.S. Patent 4,427,836. Excess ammonia (1.3 equivalents based on thetotal equivalents of methacrylic acid in the particles) was added to the hot (80-85C) dispersion between the polymerizaton of shell II and shell III to convert the acid-rich core to the ammonium salt causing the core to swell with water.
The final particle sizes averaged 400-550 nm and the solid content of the dispersions ranged from 32-43% by weight. All of the dispersions were diluted with water to 20% solids by weight to give the final liquid marking composition.
Table 1.1: Co~ >o~:Lul.s of the Voided Latex Polymers 1 part core*//9 parts(20BMA/78 MMA/2MAA)(Shell l)//x parts(Shell Il) //y parts(Shell III) ~140 nm,5BA/55MMA/40MAA
Voided Latex ShellII Shellm Particles x , - -- y I "o ~iLu 1 C 22.5 100Sty 22.5 100Sty 2Ç 22.5 100Sty 22.5 60Sty/40DVB-55 3C 22.5 100Sty 22.5 75Sty/25ALMA
4C 22.5 100Sty 22.5 85Sty/15ALMA
90MMA/lOSty 20 75MMA/lOSty/15ALMA
6 4 100Sty 9 40Sty/60DVB-55 Notes: The suffix "C" denotes a ~u~ a~dlive.
Abbreviations MMA methyl methacrylate BMA butyl methacrylate BA butyl acrylate MAA methacrylic acid Sty styrene DVB-55 Dow 55% grade of divi~yll~lzene where most of remainder is ethylvi,lylbenzene ALMA allyl methacrylate EXAMPLE2. PERFORMANCE ~ G
Markers contAining the formulations made in accordance with Example 1 were tested for erasability, burni~hing and opacity by marking on both a slatechalkboard and a composition chalkboard at both one cycle and 50 cycles. One cycle is covering a 1-inch-by-2-inch rectangle on the chalkboard surface and erasing the marking using a conventional chalkboard eraser. Fifty cycles is repeating the process 50 times.
Erasability T~tin$
The erasability of each formulation was judged by how well it could be removed, using a conventional chalkboard eraser, in comparison to the erasability of a similar marking made using conventional calcium carbonate chalk. The results are shown in Table 2.1.
Bnrni~hing Testing The burni~hing of each formulation was judged by how much gl~7ing of the chalkboard surface appeared which was not a result of physical abrasion.
The results are shown in Table 2.1.
Opacity T~
The opacity of each formulation was judged by how well the marking developed solid whiteness when dry. The results are shown in Table 2.1.
Table 2.1: pPrfon~ P Results Formul^~inn ~ e Erasability Bl; .. ;~l.;.. ~. Opacity Voided Latex Polymer lC ghosting -- fail yes--fail good (white) 2C ghosting -- fail yes--fail fair (white) 3C ghosting -- fail yes--fail fair (white) 4C ghosting -- fail yes - fail good (white) good (no ~,l,o~li,.g) no--pass good (blue-white) --pass 6 good(noghosting) no-pass good (white) --pass The results indicate that formulations containing voided latex particles having an shell polymerized from either:
(1) at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer; or (2) at least about 5% by weight, based on the weight of the shell, of a crosslinking comonomer, when at least about 50% by weight of methyl methacrylate is used as a comonomer in the shell exhibit good erasability (no ghosting) while mAintAining the opacity of the coating and without producing burnishing.
Claims (13)
1. A method of improving the erasability of an erasable marking composition, comprising incorporating voided latex particles having a shell polymerized from from at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer.
2. A method of improving the erasability of an erasable marking composition, comprising incorporating voided latex particles having at least about 50% by weight of methyl methacrylate and from at least about 5% by weight, based on the weight of the shell of a crosslinking comonomer.
3. The method of claims 1 or 2 wherein said crosslinking comonomer is a comonomer selected from the group consisting of alkylene glycol diacrylates, alkylene glycol dimethacrylates, 1,3-glycerol dimethacrylate, 1,1,1-trimethylolpropane dimethacrylate, 1,1,1-trimethylol ethane diacrylate, pentaerythritol trimethacrylate, 1,2,6-hexane triacrylate, sorbitol pentamethacrylate, methylene bis-acrylamide, methylene bis-methacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl- benzene, triallyl cyanurate, divinylacetylene, divinylethane, divinyl sulfide, divinyl ether, divinyl sulfone, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyldimethylsilane, glycerol trivinyl ether, divinyl adipate, dicyclopentenyl (meth)acrylates; dicyclopentenyloxy (meth)acrylates, unsaturated esters of glycol monodicyclopentenyl ethers, allyl esters of .alpha.,.beta.-unsaturated monocarboxylic acids having terminal ethylenic unsaturation and allyl esters of .alpha.,.beta.-unsaturated dicarboxylic acids having terminal ethylenic unsaturation.
4. The method of claims 1 or 2 wherein said crosslinking comonomer is a comonomer selected from the group consisting of an allyl ester of .alpha.,.beta.-unsaturated monocarboxylic acid having terminal ethylenic unsaturation and .alpha.,.beta.-unsaturated dicarboxylic acid having terminal ethylenic unsaturation.
5. The method of claims 1 or 2 wherein said crosslinking comonomer is allyl methacrylate.
6. The method of claims 1 or 2 wherein said voided latex particles have a core formed from at least one acid-functional comonomer and wherein said shell is polymerized after the addition of a base to said core.
7. The method of claims 1 or 2 wherein said voided latex particles have a core formed from at least one amine-functional comonomer and wherein said shell is polymerized after the addition of an acid to said core.
8. The method of claims 1 or 2 wherein said voided latex particles have a solvent-swellable core and wherein said shell is polymerized after the addition of a solvent to said core.
9. An improved liquid marking composition, wherein the improvement comprises incorporating voided latex particles having a shell polymerized from from at least about 25% by weight, based on the weight of the shell, of a crosslinking comonomer.
10. An improved liquid marking composition, wherein the improvement comprises incorporating voided latex particles having an outermost shell formed from methyl methacrylate and from at least about 5% by weight, based on the weight of the shell of a crosslinking comonomer.
11. The composition of claims 9 or 10 wherein said crosslinking comonomer is a comonomer selected from the group consisting of alkylene glycol diacrylates, alkylene glycol dimethacrylates, 1,3-glycerol dimethacrylate, 1,1,1-trimethylolpropane dimethacrylate, 1,1,1-trimethylolethane diacrylate, pentaerythritol trimethacrylate, 1,2,6-hexane triacrylate, sorbitol pentamethacrylate, methylene bis-acrylamide, methylene bis-methacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinylacetylene, trivinyl- benzene, triallyl cyanurate, divinylacetylene, divinylethane, divinyl sulfide, divinyl ether, divinyl sulfone, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyldimethylsilane, glycerol trivinyl ether, divinyl adipate, dicyclopentenyl(meth)acrylates; dicyclopentenyloxy (meth)acrylates, unsaturated esters of glycol monodicyclopentenyl ethers, allyl esters of .alpha.,.beta.-unsaturated monocarboxylic acids having terminal ethylenic unsaturation and allyl esters of .alpha.,.beta.-unsaturated dicarboxylic acids having terminal ethylenic unsaturation.
12. The composition of claims 9 or 10 wherein said crosslinking comonomer is a comonomer selected from the group consisting of an allyl ester of .alpha.,.beta.-unsaturated monocarboxylic acid having terminal ethylenic unsaturation and .alpha.,.beta.-unsaturated dicarboxylic acid having terminal ethylenic unsaturation.
13. The composition of claims 9 or 10 wherein said crosslinking comonomer is allyl methacrylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/206,303 | 1994-03-03 | ||
| US08/206,303 US5447560A (en) | 1994-03-03 | 1994-03-03 | Method for improving erasability or erasable marking compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2143359A1 true CA2143359A1 (en) | 1995-09-04 |
Family
ID=22765779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002143359A Abandoned CA2143359A1 (en) | 1994-03-03 | 1995-02-24 | Method for improving erasability of erasable marking compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5447560A (en) |
| EP (1) | EP0672734A1 (en) |
| JP (1) | JPH07331158A (en) |
| KR (1) | KR950032530A (en) |
| AU (1) | AU1237595A (en) |
| CA (1) | CA2143359A1 (en) |
| FI (1) | FI950834A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3989054B2 (en) * | 1996-07-29 | 2007-10-10 | 株式会社メニコン | Cleaning material for contact lenses |
| FI103894B (en) | 1997-03-05 | 1999-10-15 | Neste Oy | Process for making hollow polymer particle latex |
| EP0959176B1 (en) * | 1998-05-18 | 2012-09-05 | Rohm And Haas Company | Hollow sphere organic pigment for paper or paper coatings |
| US6011084A (en) | 1998-06-26 | 2000-01-04 | Binney & Smith Inc. | Erasable colored pencil lead |
| ATE262013T1 (en) | 1998-06-26 | 2004-04-15 | Binney & Smith Inc | ERASABLE COLOR PENCILS |
| EP1757638A1 (en) * | 2005-08-22 | 2007-02-28 | Rohm and Haas France SAS | Methods for using hollow sphere polymers |
| US10053597B2 (en) | 2013-01-18 | 2018-08-21 | Basf Se | Acrylic dispersion-based coating compositions |
| CN113661203B (en) * | 2019-04-04 | 2023-06-06 | 阿科玛股份有限公司 | Acrylic modified polymeric opacifiers for use in organic media |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1180474A (en) * | 1979-06-26 | 1985-01-02 | Alexander Kowalski | Sequential heteropolymer dispersion and a particulate material obtainable therefrom useful in coating compositions as a thickening and/or opacifying agent |
| US4427836A (en) * | 1980-06-12 | 1984-01-24 | Rohm And Haas Company | Sequential heteropolymer dispersion and a particulate material obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent |
| GB2103636B (en) * | 1981-08-07 | 1985-05-09 | Mitsubishi Pencil Co | Writing medium for ball point writing instrument |
| US4594363A (en) * | 1985-01-11 | 1986-06-10 | Rohm And Haas Company | Production of core-sheath polymer particles containing voids, resulting product and use |
| US4677003A (en) * | 1985-04-30 | 1987-06-30 | Rohm And Haas Company | Microsuspension process for preparing solvent core sequential polymer dispersion |
| JPH05125127A (en) * | 1985-11-28 | 1993-05-21 | Japan Synthetic Rubber Co Ltd | Polymer granule having single inner pore |
| US4940628A (en) * | 1986-09-15 | 1990-07-10 | The Gillette Company | Erasable system including marking surface and erasable ink composition |
| US4988123A (en) * | 1986-09-15 | 1991-01-29 | The Gillette Company | Erasable system including marking surface and erasable ink composition |
| US5217255A (en) * | 1986-09-15 | 1993-06-08 | Lin Nan J | Erasable system including marking surface and erasable ink composition |
| CA1298013C (en) * | 1986-11-06 | 1992-03-24 | Martin Vogel | Process for preparing core-shell particle dispersions |
| GB8718036D0 (en) * | 1987-07-30 | 1987-09-03 | Tioxide Group Plc | Polymeric particles |
| JP2774300B2 (en) * | 1988-02-19 | 1998-07-09 | 旭化成工業株式会社 | Foamable polymer emulsion composition |
| WO1989008134A1 (en) * | 1988-02-26 | 1989-09-08 | Sakura Color Products Corporation | Erasable ink composition |
| US4970241A (en) * | 1988-05-20 | 1990-11-13 | Rohm And Haas Company | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
| JP2706960B2 (en) * | 1988-11-15 | 1998-01-28 | 株式会社サクラクレパス | Water-based marking pen ink composition for neon boards |
| JP2986482B2 (en) * | 1989-08-16 | 1999-12-06 | 旭化成工業株式会社 | Amphoteric hollow polymer particles, method for producing the same, and paper coating composition using the particles |
| JPH0374440A (en) * | 1989-08-16 | 1991-03-29 | Asahi Chem Ind Co Ltd | Cationic hollow polymer particle, production thereof and filled paper using the same particle |
| JPH03227323A (en) * | 1989-12-22 | 1991-10-08 | Asahi Chem Ind Co Ltd | Production of hollow polymer emulsion and polymer grain |
| JPH03237171A (en) * | 1990-02-13 | 1991-10-23 | Sakura Color Prod Corp | Erasable aqueous ink composition |
| JP2871008B2 (en) * | 1990-06-30 | 1999-03-17 | ぺんてる株式会社 | Correction fluid |
| JP3049140B2 (en) * | 1992-01-17 | 2000-06-05 | 株式会社サクラクレパス | Erasable ink composition for writing board |
| JP3075622B2 (en) * | 1992-01-17 | 2000-08-14 | 株式会社サクラクレパス | Erasable ink composition for writing board |
| US5300538A (en) * | 1992-06-02 | 1994-04-05 | The Gillette Company | Solid marking compositions |
-
1994
- 1994-03-03 US US08/206,303 patent/US5447560A/en not_active Expired - Lifetime
-
1995
- 1995-02-15 EP EP95300968A patent/EP0672734A1/en not_active Withdrawn
- 1995-02-21 AU AU12375/95A patent/AU1237595A/en not_active Abandoned
- 1995-02-23 FI FI950834A patent/FI950834A/en not_active Application Discontinuation
- 1995-02-24 CA CA002143359A patent/CA2143359A1/en not_active Abandoned
- 1995-03-02 KR KR1019950004245A patent/KR950032530A/en not_active Application Discontinuation
- 1995-03-03 JP JP7068921A patent/JPH07331158A/en not_active Withdrawn
- 1995-05-24 US US08/449,862 patent/US5494508A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU1237595A (en) | 1995-09-14 |
| FI950834A (en) | 1995-09-04 |
| EP0672734A1 (en) | 1995-09-20 |
| FI950834A0 (en) | 1995-02-23 |
| US5494508A (en) | 1996-02-27 |
| KR950032530A (en) | 1995-12-22 |
| US5447560A (en) | 1995-09-05 |
| JPH07331158A (en) | 1995-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU635490B2 (en) | Polymers comprising alkali-insoluble core/alkali-soluble shell and compositions thereof | |
| US4735990A (en) | Aqueous resin emulsion | |
| JP3125977B2 (en) | Fluorinated acrylic latex and fluorinated methacrylic latex, their mixtures, their preparation, and use as hydrophobic coatings | |
| US20190002710A1 (en) | Voided latex particles containing functionalized outer shells | |
| SI9300072A (en) | Multistage polymers | |
| JPS60181108A (en) | Polymer tackifier and manufacture | |
| US5447560A (en) | Method for improving erasability or erasable marking compositions | |
| JP3410473B2 (en) | Aqueous resin dispersion and method for producing the same | |
| CN109929067A (en) | A kind of core-shell structure acrylic acid ester emulsion and its preparation method and application | |
| US4306009A (en) | Liquid developer compositions with a vinyl polymeric gel | |
| JPS59142257A (en) | Lime paint dispersion and manufacture | |
| CN108822676A (en) | A kind of aqueous aluminium alloy baking finish and preparation method thereof | |
| JPH07150082A (en) | Aminosilane for nonbleeding aqueous liquid paper | |
| JPS5871966A (en) | Coating composition | |
| JP2612635B2 (en) | Coating composition | |
| JPS63286471A (en) | Luster composition for floor | |
| US4363863A (en) | Liquid negative developer compositions for electrostatic copying containing polymeric charge control agent | |
| KR20060072480A (en) | Method for preparing acrylic emulsion resin composition acrylic emulsion resin composition prepared thereby and aqueous paint composition comprising thereof | |
| JP3498433B2 (en) | Method for producing aqueous resin dispersion | |
| JPH07310041A (en) | Pigment dispersion paste and water-based coating composition containing the paste | |
| JPS62179504A (en) | Production of resin binder for water-based flexographic ink | |
| JPS63317571A (en) | Marking ink composition | |
| JP3271058B2 (en) | Non-aqueous pigment ink composition for writing implement and writing implement | |
| JP2817194B2 (en) | Composition for paint | |
| JP2697443B2 (en) | Polymer emulsifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |