JP2001519740A - Correction fluid - Google Patents

Abstract

  (57) [Summary] A correction fluid containing a composite material (FIG. 6) containing particles composed of the film-forming polymer (2) and the polymeric substance (8).

Description

DETAILED DESCRIPTION OF THE INVENTION                                  Correction fluid   The present invention relates to an aqueous correction fluid, a method for producing a correction fluid, and composite particles useful for the correction fluid. It is about materials.   Correction fluid can be used to cover type, writing, printing or drafting errors, etc. Can be used, for example, type, writing, drawing can be done on it when it is sufficiently dry Liquid. The fastest overwriting time of the correction fluid is due to the use of volatile organic solvents. Although better achieved, the use of such substances is for environmental reasons and In some cases, the risk of abuse has become quite undesirable. Aqueous liquid The correction fluid containing the body medium does not suffer from these disadvantages, but usually contains an organic solvent composition. It takes longer to overwrite. "Overwrite time" in this discussion refers to the applied correction fluid The following marks can be drawn on the surface of the modified pigment with polymeric material: Means the time required to achieve dimensional stability sufficiently.   U.S. Pat. No. 4,665,107 describes, for example, po Preparation of submicron-sized pigment particles encapsulated in a rimer matrix is described. Have been. The pigment particles are dispersed in the polymer solution and this mixture is dispersed in water Form an emulsion. The solution is then removed and the pigment encapsulated in the polymer Particles are formed.   U.S. Pat. No. 3,884,871 describes agglomeration of pigments in coatings. Coating pigment particles containing polymer to prevent or reduce I have. First, the fixing agent is adsorbed on the pigment particle surface, and then the organic vinyl monomer is added. It is obtained and polymerized to form a coating on the particles. The pigment particles are individually And remain submicron in size. U.S. Pat. No. 4,421,6 No. 20, No. 4,665,107, No. 3,281,344, No. 3,897,5 Nos. 86, 4,023, 981 and 4,036,652 each describe A similar method has been described in which pigment particles are encapsulated by a polymer.   U.S. Pat. No. 4,194,920 discloses an internally coloring white spherical pigment composition. Things are listed. Up to 4 microns (whether ethylenically unsaturated monomers Pigment particles are embedded in the spherical body of the organic polymer). The sphere is , Produced by aqueous emulsion polymerization. U.S. Pat. Nos. 4,264,700 and No. 4,358,388 describe particles containing magnetic particles dispersed in a polymer. A composite material is described. The particle composite material comprises a monomer in the presence of magnetic particles. It is produced by polymerizing   U.S. Pat. No. 4,254,201 discloses a pressure-sensitive toner which is a particle composite material. Is described. Each of the toner particles is, for example, a film forming material Numerous granular clusters of pressure-sensitive adhesive encapsulated with a thin and fragile coating It is a porous aggregate composed of Particles of pigment or magnetic material are used to create gaps between the granules. Trapped in aggregates between. The granules are properly readable by the spray fluid. Yes, the adhesion between the encapsulating coatings before it does not stain and does not spread on the surface of the correction fluid More adhere to each other.   The correction fluid may contain water and therefore need not be completely dry, It should be well understood that the surface is dimensionally stable enough to allow overwriting It is. Water remaining in the correction fluid at the time of overwriting then evaporates from the surface And / or disappears into the support paper. So, typically, "Overwrite "Time" occurs before the correction fluid has completely dried.   Increase the amount of solids added to reduce the overwriting time of the aqueous correction fluid ( Attempts have been made to reduce the amount of aqueous liquid therein). This technique is To some extent, but is generally the best that can be achieved by maximizing the solids loading. Short Is no longer used because the current aqueous correction fluid already has an overwrite time of . If an attempt is made to contain more solids, the dispersion may be Instability due to settling and agglomeration of the material, resulting in loss of lay-down efficiency . Addition of extra solids, e.g. fillers, can reduce the overwrite time altogether. Immediately the viscosity increases significantly. That is, the liquid becomes thicker but the overwriting time is faster. Does not go away. In fact, adding extra conventional filler to aqueous correction fluids can result in overwriting time May be increased. In short, simply changing the percentage of solids, When overwriting the current aqueous correction fluid (without adversely affecting the performance of the correction fluid) The inventors believe that it is impossible to make the interval any longer.   The inventors have developed aqueous correction by including the novel composite particles in the correction fluid. It has been found that the overwriting time of the liquid can be reduced and other improvements can be obtained.   Composed of two or more individual components that combine to form a complete unity Particles (hereinafter generally referred to as “composite particles”) are known. For example, by drying Many describing particulate composites formed by coating particles There are many patent specifications. Provide a binder in the space between the granules to improve adhesion. can do. Overall, the individual porous agglomerates are rough like orange It has a surface and is almost spherical. During use, the pressure applied to fix the toner Below, the agglomerate breaks down into discrete granules, and the encapsulating film breaks and is inside it Releases pressure sensitive adhesive.   U.S. Pat. Nos. 4,206,094 and 4,157,323 each disclose A polymer functional microparticle containing a metal and a metal compound is described. The body is made of finely divided metal or gold, such as iron, gold, platinum or magnetite. Addition polymerization of a covalent olefin monomer in the presence of a metal oxide particle , But these metal (oxide) particles are buried in the resulting microparticles I have. The microparticles are then used for labeling or separating biological cells . The addition polymerization can be performed by high energy gamma irradiation. The method is water Either an aqueous suspension polymerization method or an aqueous emulsion polymerization method.   The inventors have devised particle composites that are particularly useful for aqueous correction fluids. These particles Presence can reduce drying time and / or stabilize correction fluid And provide much higher solids loading if needed can do.   According to the first aspect of the present invention, there are provided a plurality of film-forming binder particles, Comprising a polymerized polymeric material containing a portion of the formed binder particles, wherein the film form The said part of the formed binder particles is a composite material together with the polymerized polymer material. A substance is provided for use in a correction fluid forming particles, wherein the composite material The particles, when polymerized, bind the binder particles contained in the composite material to each other. Combined, the composite material particles having a substantially spherical outer surface and from about 0.1 to about 100 Having a diameter of micrometers, and a portion of the film-forming binder particles It is bonded near the outer surface of the composite material particles.   In a second aspect, the invention relates to a method for producing a substance for use in an aqueous correction fluid. A method for providing film-forming binder particles, the method comprising: Providing the liquid, mixing the polymerizable liquid and the film-forming binder particles. Combining and polymerizing the polymerizable liquid to form a suspension of composite particles And wherein each composite material particle includes the film-forming binder particles therein. Having the polymeric material of the composite material particles in contact with the binder particles before The binder particles are fixed to each other, and a part of the film-forming binder particles is The composite material particles are bonded near an outer surface thereof, wherein the composite material particles are about 0.1 It has a diameter of about 100 micrometers.   In another aspect, the invention is directed to (A) comprising at least one film-forming binder particle suspended in an aqueous medium. Aqueous latex, (B) milky particles, and (C) Substance of the present invention Wherein the milky particles and the substance are in suspension in the medium. Provide correction fluid.   In a further aspect of the invention, (A) an aqueous solution containing at least one film-forming binder particle; Dispersing in a positive solution, (B) polymerizing the polymerizable liquid to form an aqueous suspension of composite material particles. Thus, the polymeric material comes into contact with a part of the film-forming binder particles and Fixing each other with respect to each other to form the composite material particles, and (C) adding the aqueous suspension to a further correction fluid A method for producing an improved correction fluid comprising:   Preferably, in this method, (D) said composite particles have a substantially spherical outer surface; (E) the outer surface comprises some of the particles of a film-forming binder; (F) the composite material particles have a diameter in the range of about 0.1 to about 100 micrometers; It is size. The film-forming binder particles are of course smaller than the composite material particles. Please.   In a further aspect, the present invention provides a container for correction fluid, dispensing the correction fluid from the container. Outlet for dispensing and applicator for spreading dispensed liquid under shear stress A correction fluid applicator, comprising an edge shear member integral with the fluid.   The present invention provides a step of providing the correction liquid of the present invention and a step of applying the correction liquid to a surface. And coating the surface with a correction fluid.   The particles of the composite material according to the invention each comprise at least one film-forming binder. Comprising a plurality (meaning at least two) of smaller particles, wherein The particles are bonded to each other and form a polymer formed by the polymerization of a polymerizable liquid. Are fixed to each other. This polymer is crosslinked. The composite material grain The child may include other low solids particles such as milky particles, for example, pigments. one Generally, within each composite particle, the plurality of smaller particles are very close to each other or even Or contact, the polymer formed from the irradiated polymerizable liquid Fill the voids or gaps between the particles. In this way, smaller particles The cured polymer bonds together and is fixed relative to each other. Adjacent bar Due to the surface entanglement process between the inner particles, some binder particles Binding can occur such that it can be directly bound to The inventors call the entanglement process In other words, the polymer chain extending from the surface of the binder particle is adjacent to the binder Meaning that similar chains and entangled binder particles extending from the particles are bound together. To taste.   The composite material particles have a film-forming binder particle on an outer surface thereof. In addition, it is preferable that binder particles are partially or wholly included in the composite particles. The outer surface of each particle of the composite material is substantially spherical, i.e., the composite particles Mostly round and substantially borderless, it promotes close packing in the coating. New features of the present invention The sign lies in the compression of the binder particles and composite particles when the correction fluid is applied. felt.   The particles of the composite material according to the invention are generally relatively small compared to their volume. Has surface area. They are generally non-porous and generally contain an aqueous suspension of correction fluid. Relatively non-adsorbent to turbid media. Note that they are generally relatively smooth Has a surface.   The size (diameter) of the composite particles is usually in the range of 0.1 to 100 micrometers. And preferably 0.1 to 50 micrometers, but the average size of the composite particles is large. The size is about 20 to 30 micrometers. We use the term average particle size Where 50% of the sample is smaller and 50% means larger particle size. This value is also known as the median diameter. The use of the correction fluid of the present invention involves complex The material particles are generally made up of the milky particles and film forming vias commonly used in aqueous correction fluids. Larger than under particles. Thus, for example, about 0.5 micron milky white With particles and film-forming binder particles, the size is about 20 micrometers A typical composite material particle has about 50,0% smaller binder particles therein. 00 included.   We have found that the particle size distribution of the composite material particles is about one order of magnitude or more (micrometers). (Indicated by the letter) is convenient (although not required). Thus, for example, if the composite particles have an average particle size of about 20 micrometers, If so, the composite particles may range in size, for example, from about 0.1 to about 50 micrometers. It is preferred that This promotes a good filling of the particles during the application of the correction fluid It is also believed to contribute to the particularly preferred fast-setting effect described below. Said The composite material particles are preferably at least 10 times the size of the film forming binder particles. Preferably, it is up to about 100 times. Further, the milky particles are usually The size is the same as that of the film-forming binder particles.   More specifically, the composite material particles of the present invention are used for correction fluids. The radiation-polymerizable liquid as at least one coating form as a number of independent volumes Disperse in aqueous latex of synthetic binder and then polymerize by irradiating the liquid It is preferable to make it. This method uses polymerizable liquid globules that are in phase with the medium. Suspended and polymerized in a medium without interaction to produce polymerized "small spheres" It is not the same as the conventional suspension polymerization method. In the present invention, the polymerizable liquid is independently dispersed. The volume is not present in the latex in the form of spherical globules and is surprisingly flat. It is a thin plate shape. For example, the volume is generally from an oval to a ribbon. A shape on a disk may be used. The size may vary, but the inventors consider the volume The body is about 1-6 micrometers thick and about 5-20 micrometers Prefer to have "diameter" or length. Smaller or larger volume Can also be used. The shape and size of these independent dispersed volumes What is the shape (generally spherical) and size (larger) of the composite particles formed from Very different. The space between the independent dispersed volumes of polymerizable liquid is coated There is an aqueous latex of binder particles. FIG. 2 of the accompanying drawings shows the dispersion before polymerization. Represents the body and is described in more detail below.   Upon irradiation, the dispersed volume of the polymerizable liquid polymerizes and is adjacent to the polymerizable liquid. The contacting volumes combine to form composite material particles mixed with film-forming binder particles. Form. The resulting composite particles are an independent, dispersed, lamellar volume of polymerizable liquid. Much larger than. For example, in the form of an independent, dispersed, lamellar volume of polymerizable liquid The size is 5-20 micrometers in length, 1-6 micrometers in thickness (more (Small volumes also exist), but the size of the composite particles is usually about 100 mm in diameter. It is up to the icrometer. The composite particles are generally non-uniform and have a film forming barrier. A cured polymer formed from an irradiation polymerizable liquid, having an inner particle therein; In addition to having limers, it may also have other particles such as milky particles. Composite Material particles are contained in the film-forming binder exposed on the surface of the composite particles. With particles.   The method of the invention in which composite particles are made is distinguished from conventional emulsion polymerization methods Should. In such conventional methods, the initiator dissolved in the aqueous layer is a water-insoluble monomer. Some of the mer enters the solubilized surfactant micelles and initiates polymerization there I do. In contrast, in the irradiation method of the present invention, the monomer volume dispersed in the aqueous layer is used. Polymerization occurs in the stack.   The composite particles of the present invention are used in aqueous correction fluids. For example, they already live In addition to the correction fluids that have been made, the amount of solids added can be increased, Is mixed with a compatible film-forming latex material and / or opacifier to form a correction fluid You can also. The inventors use the term "compatible film-forming latex material" With a polarity not opposite to that of the film-forming binder particles used in the composite material particles Means Therefore, the composite particles are mixed with the non-ionic film-forming latex. The composite particles can be made from nonionic or anionic film-forming latex If so, it can be mixed only with the anionic film-forming latex. same Similarly, when the composite particles are made of a cationic film-forming latex, Incompatible with on-film-forming latex.   However, instead of using the composite particles of the present invention as described above, the inventors: I prefer to make the composite particles as is in the correction fluid. This is a radiation polymerizable liquid Is dispersed in a correction liquid and then irradiated. If you do this, The film-forming binder particles in the composite material are the film-forming binder of the correction fluid itself. Same as particles, and therefore compatible. If this is done, the resulting fix The liquid contains too little free film forming binder (meaning the inventors "Free film-forming binder" refers to a film form that is not part of the composite material particles Formed on the support and adhered when dried. I can't do it. The coating tends to shatter and flake off the paper. composite Before the material particles are produced, the amount of film-forming binder in the correction fluid The results are not very satisfactory even if the concentration is increased above normal. Only And a correction fluid with a compatible film-forming binder (untreated and unirradiated) When the amount of the film-forming binder is increased after irradiation, such as by further adding, The results are very favorable as discussed below.   According to the present invention, a film-forming binder for preparing the composite material particles of the present invention Is the same as the film-forming binder of the further correction fluid mixed with the suspension in step (c) Preferably, or similar. This ensures a stable dispersion and good Ensure the compatibility desired to achieve film formation. Two film-forming vines It is not necessary (although preferably) that the enders be identical. Two compatible bikes If they can be satisfactorily coalesced during film formation, Is enough.   In the method for producing composite material particles of the present invention, the irradiation polymerizable liquid is at least Are also dispersed in an aqueous latex of one film forming binder and then polymerized. The radiation polymerizable liquid is a liquid monomer (at room temperature) containing ethylenic unsaturation. Or an oligomer. When exposed to irradiation, said monomer or oligomer Performs addition polymerization due to ethylenic unsaturation. Many irradiation polymerizable liquids can be used is there. We have found that acrylate and methacrylate monomers, especially Nord A propyl dimethacrylate (London Resin Company (London, UK) (Commercially available as Hi-Tad). Another specific example is ethylene glycol. Cole dimethacrylate, triethylene glycol dimethacrylate, tetra There is tylene glycol dimethacrylate. More generally, the following groups Irradiation polymerizable monomers or oligomers are preferred. That is, bisphenol A Aliphatic urethane dimethacrylate, bisphenol A aliphatic epoxy dimethacrylate And bisphenol A aliphatic ester dimethacrylate. Suitable Specific examples of the irradiation polymerizable liquid are as follows. These are Cray Valley (France) It is commercially available from La Defense, Paris, 92970) and the name of the catalog is in parentheses. It is shown in a)Epoxy acrylate gommer Standard bisphenol A epoxy diacrylate (CN104) Epoxidized soybean oil diacrylate (CN111) b)Urethane acrylate ligomer Aliphatic urethane triacrylate (CN931 A60) Aromatic urethane triacrylate (CN970 A60) c)Oligo acrylate Tris (2-hydroxyethyl) isocyanurate triacrylate (SR 368) d)Oligoether acrylate Polyethylene glycol 400 diacrylate (SR 344) Ethoxylated trimethylopropane triacrylate (SR 454) Ethoxylated pentaerythritol tetraacrylate (SR494) e)Bifunctional acrylate monomer Tripropylene glycol diacrylate (SR 306) f)Trifunctional acrylate monomer Trimethylolpropane triacrylate (SR 351)   Other examples include dipentaerythritol hexaacrylate and aromatic urea. There are urethane acrylates.   The amount of irradiation polymerizable liquid used depends on the aqueous latex of the film-forming binder particles. When dispersed, must not be so numerous that, upon irradiation, the dispersion transforms into a solid mass No. In any case, it will be possible to find the optimum amount through routine trials and experiments. Can be. If the latex is in the correction fluid, the amount of radiation polymerizable liquid used Generally, less than about 50% by weight of the mixture of the irradiation polymerizable liquid and the other components of the correction fluid. The inventors have found what must be done. Of course, the amount of irradiation polymerizable liquid Determine the amount of composite particles in the particle suspension resulting from the polymerization.   The irradiated polymerizable liquid is homogeneous throughout the aqueous latex of the film-forming binder before polymerization. Is preferably dispersed in This is the Disperm at mixer). Above As such, the independent volume of irradiated polymerizable liquid is not in the form of globules, but rather Of flat lamella, for example disc-like or pancake-like, in aqueous latex Exists in shape.   In the method for producing the composite material particles of the present invention, the irradiation polymerizable liquid (monomer or Oligomers) are exposed to light, ie, exposure to light, electron beams, microwaves or gamma rays. Polymerized by dew. We can use light (using a photoinitiator) or more preferably They prefer to use electron beam irradiation. The dose required for polymerization to occur Depending on the monomers or oligomers to be polymerized and the overall system, about 10 Electron beam dose up to Mrad is satisfactory for Hi-Tad and similar substances I know it is.   The correction fluid of the present invention contains, in addition to the composite material particles of the present invention, milky particles and a film-forming bath. Contains inders.   The milky particles used in the correction fluid of the present invention may be any pigment suitable for the purpose. Well, the most common is titanium dioxide. If a color other than white is needed, Other pigments or colorants may be included to provide the desired effect. Generally, milky The particles have an average particle size of less than 0.8 micrometers (to increase dispersibility); The particles are made of alumina or a combination of alumina and silica to increase dispersibility. It may be pre-processed.   The amount of milky particles in the correction fluid of the present invention is generally 20 to 70% by weight, preferably 25 to 60% by weight, most preferably 30 to 50% by weight. Preferably, Has an average particle size of about 0.4 micrometers or less. Suitable dioxide dioxide Tan pigments include commercially available rutile titanium dioxide and anatase titanium dioxide. Or blends or mixtures of these, which are about 0.2 micrometers Average particle size of from 0.4 to 0.4 micrometers and an average absorption of about 16 g / 100 g pigment. It is preferable to have an oil amount. One preferred titanium dioxide is a rutile-type titanium dioxide produced by a chlorination method. Ti-Pure R-900 (DuPont, Wilmington, Del., USA) Yes (Ti-Pure is a registered trademark). This composition comprises about 94% titanium dioxide and 4. Contains 8% alumina. Although the particle size varies, 80% of the particles Less than an ichometer, 90% of the particles are less than 0.6 micrometers . Other suitable titanium dioxide compositions include Ti-Pure R-901, Ti-Pure R-902, Ti-Pur e R-931, Tioxide R-XL (Tioxide America, Inc., Columbia, Maryland, USA) ) And Kronos 2131 (Kronos, Inc. (Houston, TX, USA)). other May be used alone or, preferably, in combination with titanium dioxide. No. Such pigments include zinc sulfide and zinc oxide.   The film-forming binder used in the composite material particles of the present invention and the correction liquid of the present invention is: Polyester that loses aqueous suspension medium or solvent at room temperature to form a continuous, adherent coating Any natural or synthetic polymer can be used. The film-forming vine Preferably, the dust particles consist only of the film-forming binder.   Examples of suitable film-forming binders include: a) Copoly of 40% styrene / 55% ethyl acrylate / 5% divinylbenzene Styrene acrylic copolymer such as mer b) Copo 40% styrene / 55% butyl methacrylate / 5% divinylbenzene Styrene methacrylic copolymers such as Limmer (and UCAR products referred to below) quality) c) such as a copolymer of 8-25% ethylene and 92-75% vinyl acetate Ethylene vinyl acetate copolymer d) vinyl acrylic resin such as 60% vinyl acetate / 40% styrene copolymer Remar e) 70% methyl methacrylate / 28% ethyl acrylate / 2% divinylbenze Acrylic polymers such as copolymers of f) polymers of vinyl acetate or vinyl alcohol such as polyvinyl acetic acid and Copolymer g) Polyurethane (Witco polymer described below) h) 75% methyl methacrylate / 25% dimethylaminoethyl methacrylate Cationic methacrylate copolymers such as copolymers There is.   The film-forming binder is an aqueous latex, i.e., a film-forming binder particle. The particles are used in the form of a dispersion in which the particles are dispersed in an aqueous suspension medium. It is small enough to be suspended as a result of the round motion. Generally, the particles Is less than about 10 micrometers (diameter), more typically 1 micron in diameter Is less than. The composite material particles of the present invention are used to form an aqueous latex of a film-forming binder. When the polymerizable liquid is made by dispersing and irradiating the polymerizable liquid, at least Some, and sometimes most, of the film-forming binder particles are Become included in the child. Film-forming binder particles that do not become part of the composite particles The offspring are free and in suspension.   Most of the water-soluble dyes used in aqueous inks are negatively charged. Anion And / or non-ionically stable film-forming binder dispersions and pigments When using an aqueous correction fluid containing these, these water-soluble dyes bleed into the correction layer. , Leading to the formation of unsatisfactory modifications. Anionic to prevent dye bleed Interacts with dye molecules and makes them insoluble so that they cannot diffuse through the modification The cationic species may be included in the formulation as an anti-bleeding agent. This bleed prevention Stoppers are cationic film-forming polymers such as Worleecryl 8721 (Worlee Chemie GmBH (Hamburg, Germany)), cationic non-film-forming polymers such as Rhoplex R PR- Complexes with 26 (Rohm & Haas (Philadelphia, USA)) or an anionic dye And non-polymerizable cationic species that render them insoluble. Works like this Examples of materials include UK Patent Application No. 9211760.5 (herein incorporated by reference). Quaternary ammonium compounds of the type described in For example, 1,2-ethylenediaminium-N, N'-ditetradecyl-N, N , N ', N'-tetramethyldibromide.   The dispersion of the film-forming binder dispersed in water is stabilized by adding a surfactant Is done. The surfactant may be anionic, cationic or non-ionic. It is ionic. Prevents interactions that could lead to polymer dispersion instability Therefore, it is important that the charge carried by the surfactant is compatible with the charges of other species in the liquid. It is important. Most available film-forming polymer dispersions are anionically stable And are unsuitable for use with cationic anti-bleeding agents. Advantageously, the film-forming binder is stabilized with a cationic surfactant. An example As Vinamul 90045 (vinyl acetate / dimethylaminoethyl methacrylate Copolymers) (sold by Vinamul Ltd. (Carleton, Sleigh, UK)), Witcobon d Polyurethane manufactured by W-2123 (Witco Corporation, Chicago, Illinois, USA) ), Primal LE-1126 (or E-1179N or E-1242) (Rohm & Haas Company (UK) Self-crosslinking acrylic emulsion manufactured by London) and Vinac XX210 (or Or XX220, XX230 or XX240) (All Air Products (Ale, Pennsylvania, USA) (Vinyl acetate homopolymer emulsion) manufactured by Intown. Non-ionic Examples of systems include Vinamul 6955 (vinyl acetate / Veova Shell Chemicals / other Refin) and Vinamul 6975 (vinyl acetate / Veova).   We describe certain correction fluids of the invention that are very fast setting in detail below. You. In these liquids we have formed a soft film that gives a soft film. The binder, ie the film-forming binder, has a glass transition temperature of less than 12 ° C. It is preferred to use a film-forming binder latex. But especially in the fast setting In the case of no correction fluid according to the invention, two or more film-forming binders are used. It may be convenient to include it in the latex. Thus, for example, correction fluid Are soft and hard film forming binders (i.e. Binder having a glass transition temperature of more than The correction fluid is If the glass transition temperature of the film forming binder is between 10 ° C. and 17 ° C., Only one forming binder may be included.   Preferred soft film-forming binders have a glass transition temperature of less than 10 ° C You. As a film-forming binder having a glass transition temperature of less than 12 ° C., styrene-a Kuryl copolymer, styrene methacrylic copolymer, ethylene-vinyl acetate copolymer There are limers, vinyl acrylic polymers and acrylic polymers. As a specific example Is UCAR^R Latex 446 (Tg = 9 ° C) (Union Carbide (Ke, North Carolina, USA) Illy)), UCAR^R 100,76 RES 4170 (Rohrn & Haas Company, Pennsylvania, USA Manufactured by Philadelphia, Ala.), Airflex 426 (Air Products, Pennsylvania, USA) Allentown, A) Manufacturing), UCAR^R 354 and UCAR^R There are 415. UCAR^R Latex446 Is a particularly preferred film-forming binder having a low glass transition temperature. Non-ionic Stabilized is a latex containing a synthetic acrylate / styrene polymer. It is a liquid emulsion. UCAR^R Latex 446 has approximately 38% water and 62% Methyl acrylate, butyl acrylate, styrene, methacrylic acid and 2-hydride Contains a roxyethyl acrylate copolymer. In addition, about 0.03% Contains aldehyde and 0.02% ammonia. Generally desired for coatings Soft film shape required in correction fluid to give softness and flexibility The amount of the binder is between about 2 and about 12% by weight (more preferably between about 4% and about 9% by weight).   Hard film-forming binders include, for example, styrene acrylic copolymers, styrene Methacryl copolymer, ethylene-vinyl acetate copolymer, vinyl acrylic and And acrylic. For example, UCAR^R Latex 144 ((Union Carbide) Tg = 20 ° C), UCAR^R 503, UCAR^R 422, and UCAR^R There are 51. UCAR^R Latex 144 is especially good Good. UCAR^R 144 is about 52% water and 48% butyl acrylate, styrene And methacrylic acid copolymers. It also contains about 0.1% ammonia. The amount of hard film forming binder used should be such as to give the film hardness as desired. Quantity. Generally, the amount of hard film-forming binder present in the correction fluid is about 3 Between about 4% and about 12% by weight (more preferably between about 4% and about 9% by weight). You. Preferred weight ratio of hard film-forming binder to soft film-forming binder ( On a dry basis, i.e., for each solids pigment), from about 70:30 to about 20:80. And more preferably between about 40:60 and about 60:40.   The correction fluid of the present invention preferably has a viscosity between about 50 and 500 mPa s, more preferably Has a viscosity between about 80 and 300 mPa s (50 s^-1(Measured in shear) Is preferred. The correction fluid applied with a brush is at least 60%, more preferably Preferably has a total solids content of at least 65%. The emergency listed below Fast-setting liquids usually have a solids content of more than 70%. The correction fluid of the present invention comprises 1 Preferably, it also contains one or more dispersants and surfactants.   Whole white particles (including extender, colorant, etc.) for the film-forming binder The preferred ratio is preferably between about 5: 1 and about 3: 1, more preferably about 4: 1: Between 1 and about 3.7: 1.   The correction fluid of the present invention contains needle-like particles for dimensionally stabilizing the resulting film. May be included. Preferred acicular particles have a length of less than about 0.1 mm and a length of about 15: Aspect ratio between 1 and about 2: 1, more preferably between about 5: 1 and about 10: 1 (The aspect ratio is the ratio of large dimensions to small dimensions. Is). Particularly preferred acicular particles are composed of calcium metasilicate, NYAD4 (NYCO Minerals, Inc., Wisconsin, NY, USA) Rusbro)). Preferably, the correction fluid is between about 0.5% and about 9% by weight (more More preferably between about 1% and 5%).   Preferred pigment dispersions of the above anionically stable systems are Nopcosperse^R 44 (H enkel Corp. (Ambler, PA, USA)) Sodium salt of the proton electrolyte or preferably the sodium salt of the maleic anhydride copolymer Um salt, such as TAMOL^R  731 SD (Rohm & Haas, Philadelphia, PA, USA Fear)) or the sodium salt of polymethacrylic acid. In cationic systems Preferred dispersants are Hipochem CGB (High Point Chemical Corp., North America, USA) Aliphatic quaternary compounds such as High Point, Carolina). The dispersion The agent can be used to remove large amounts of pigment in the correction fluid with low viscosity and little or no foam formation. Must be added in sufficient quantities to ensure complete dispersion. other Preferred polyelectrolyte acrylate dispersants (for anionically stabilized systems) The TAMOL^R There are 850 or 950. Preferably, the correction fluid is 0.5% by weight. ~ 1.5% by weight, more preferably O.I. 8% to 1.1% by weight of dispersant No.   The surfactant acts as a wetting agent. Any suitable surfactant But can be used. Preferred surfactants are non-ionic and 2,4,7,9-te Surfynol, a tramethyl-5-decyne-4,7-diol^R 104 (Air Product s and Chemicals, Inc. (Allentown, PA, USA) Diols and alcohols. Preferably, the correction fluid has about 0.3 weight % To about 2.0% by weight, more preferably 0.44% to 1.5% by weight of surfactant Contains sexual agents.   The correction fluid may include an extender pigment. Preferred extenders include 97% More than kaolin clay (Al_TwoO_Three. 2SiO_Two. 2H_TwoO) less than 3% water and 0 . Kaopaque with 35% sodium polyacrylate / soda ash dispersant^R Ten -S (Dry Branch Kaolin Co. (Drive Ranch, Georgia, USA)) ("China") clay. Other preferred kaolin clays include NcNamee Clay (R.T. Vanderbilt, Inc. (Norwalk, CT, USA)) and Huber 40C (J.M.Hub er Corp. (Macon, Georgia, USA). The extender pigment is It is added in an amount that enhances the ability to write with ballpoint pen ink on top of. Preferably, The correction fluid comprises 5% to 15% by weight, more preferably 5% to 10% by weight, It must contain an extender pigment.   For example, standard color matching technology is used to match lined notebook paper. The primary pigment of titanium dioxide with other pigments such as black, baked amber and blue. Can be opened. Preferred black pigments are aqueous dispersible carbons such as Mars Black Black. Preferred baked amber pigments are Burnt Umber W-3247, Aurasperse^R (Engelhard Chemical. (New Jersey, USA)). These colorants The correction fluid is used in an amount that matches the white tint of the paper used. Of course, colored You can also make a colored correction fluid for this paper. Preferably, the correction fluid is 2 . Contains less than 0% by weight of colorant pigment.   The correction fluid may contain a biocide. The biocide causes bacteria to contaminate the correction fluid Used to prevent Bacteria attack certain polymers, but make correction fluid Some components used to produce, for example, pigments, And many. Sufficient amounts should be used to prevent bacterial growth. Preferably The correction fluid contains about 0.05% to 1.0% by weight of the biocide. Biocide sex Quality is not important. Examples include fluorinated sulfonamides, organic amides and fats There are acid-modified amides. As a specific example, 1,2-benzisothiazoline-3-O There is a   The correction fluid may contain an antifoaming agent. Antifoam typically used in correction fluids Can be used, but preferred antifoaming agents include Napco^R 8034 (Henkel Corp. (Ambler, PA, USA)). Such defoamers are usually A mineral oil derivative mixed with amorphous silica. Must be mixed in amounts to ensure that they are not present. Preferably, the correction fluid is 0.05% to 1.0% by weight, more preferably 0.21% to 0.4% by weight. It contains% by weight of an antifoaming agent.   The aqueous suspension of the correction fluid of the invention and the composite material particles of the invention are dispersed in a suspending medium. Solid particles (composite particles). The medium may be water alone or water And one or more other liquids, such as methanol, ethanol or Alcohol such as propanol or 2-methoxyethanol or 2-ethoxy It may be a mixture with a glycol ether such as ciethanol. The medium is dissolved Materials, such as dispersant polymers, chelates for dyes, and soluble film-forming binders Or a surfactant or the like. Amount of aqueous suspension medium in the correction fluid of the present invention Is generally less than 15% to 40%, preferably about 15% to 30%.   The correction fluid of the present invention can generally be manufactured in several ways. For example The respective components can be mixed in any order or combination. But already As described in the above, the inventors made the composite material particles as they were in the correction fluid, Add a film-forming binder with (eg, containing a compatible film-forming binder). Further correction fluid). Also, the present invention is not limited to irradiation polymerized substances. Should be understood. Irradiation polymerization is most preferred, but it produces composite material particles. All methods of making are included within the scope of the present invention.   In accordance with a preferred practice of the present invention, the inventors have determined that at least one film-forming binder Polymerization of the irradiation polymerizable liquid in a correction liquid containing Surprisingly, liquid destabilization and unacceptable viscosity increase In addition, it has been found that the solid content of the correction fluid can be significantly increased. . This is due, in part, to the nature of the composite particles formed by the polymerization of the liquid. so Yes, especially when the composite particles contain a film-forming binder and possibly (radiation polymerizable liquid) (Combined by polymer formed by irradiation of body) This is due to the fact that it incorporates other components, which essentially adds each component to the system. The inventors think that it is adapted. In particular, in this method, the irradiation polymerizable liquid Into a dispersion containing a latex of a film-forming binder and a high solids content. Can be dispersed and irradiated to produce the composite material particles of the invention, and the resulting dispersion The liquor is stable and contains a much higher solids loading than before.   Accordingly, the present invention relates to a dispersion comprising an aqueous latex of a film-forming binder. The amount of solids added to the liquid should be increased without loss of stability and A technique for use in correction fluids that can be increased without incurring the expected increase in viscosity. Provide art. Thus, the present invention is more efficient than was possible with the prior art. High solids content in the correction fluid without destabilization and unacceptable increase in viscosity. Provide a way to provide. In particular, the maximum solid content of the conventionally known aqueous correction fluid is about 7 2% but up to about 85% or more solids addition according to the invention Amount can be achieved. It is not known why high solids loading substances remain liquids suitable for use. Although not described, one explanation is that the almost spherical binder near the surface of the composite particles The dirt particles provide additional lubricity between the composite particles. Also, play The release binder particles are electrically charged, so the pressure It stays separated until it comes into contact with each other or with the composite particles. Further, an aqueous layer 6 between the composite particles containing the binder particles 2 (see FIG. 3 described below) ) Increases the lubricity between the composite particles and allows liquids to be added even at very high solids loadings. Maintains the composition of the body state. These high solids liquids according to the invention are generally Has a shorter overwrite time than previously known conventional correction fluids, almost instantaneous Some show a curing effect.   The aqueous correction fluid of the present invention has a normal overwriting time of the aqueous correction fluid, for example, about 40 seconds or Can be formulated to have a longer overwrite time. But higher By using a high solids content and / or a high ratio of the composite material particles of the present invention, As a result, the overwriting time can be significantly reduced. The inventors have found that less than 30 seconds, Preferably, an overwrite time of less than 15 seconds, most preferably less than 10 seconds. Actual According to a highly preferred feature of the invention, the liquid comprises a correction liquid on paper or other support. There is virtually no delay between applying to the body and applying the overwrite to it Can be prescribed as follows. Such liquids are unique, their preparation method and In itself, it constitutes a further aspect of the present invention (the `` overwrite time '' is In the world, when writing with a writing instrument, make sure that the tip of writing in the correction fluid is not scratched. Means that the quality and readability of the laydown is equal to the laydown on paper It is understood that. Writing utensils such as ballpoint pens are clean, soft and sticky Do not pick up damaged correction coatings. One test procedure to measure overwrite time is an example Described below in connection).   Thus, the present invention provides an aqueous suspension medium and milky particles dispersed in said medium, Includes correction fluid comprising film-forming binder particles and composite material particles of the present invention When the liquid is spread as a layer on a support, the layer is solidified. Converts to a substantially non-tacky layer in form within 10 seconds, most preferably substantially immediately Is what you do.   Laying down the layer (or coating) of correction fluid onto paper (or other support) and The actual time between the ability to accept overrides is substantially zero (ie, Not) to the desired time. The actual time will be The other components of the liquid, along with the weight and the proportion of composite particles of the invention present (In general, the higher the solids content, and / or The higher the ratio of the composite material particles, the shorter the overwriting time.) Very ordinary trial Through liquid and experimentation, formulate liquids to give maximum quality in a particular situation. You can choose. Generally it is preferable to have the shortest overwrite time possible Therefore, a further description of the present invention is directed to the correction fluid of the present invention which provides a minimal overwrite time. Although the present invention aims to include a correction fluid having a longer overwriting time, I want to be understood.   Highly preferred quick-setting correction fluids of the present invention are directly spread on paper or other support. After 1 or 2 seconds, a solid film is formed. In addition, the liquid placed on paper The whole body becomes solid as soon as it spreads or shortly thereafter. Therefore, before When a drop of the liquid is placed on the support, the substance remains liquid until spread. And while substantially expanding, the substance accepts overwriting by a writing instrument. All to a dimensionally stable material that can be used. The substance is considered to be solid Typically, it hardens sufficiently. While spreading said liquid substance on the support The composite material particles therein are not destroyed and remain substantially intact. Other exist Together with the particles, the composite particles form a tightly packed and cured material.   In contrast to previously known aqueous correction fluids, the solidification or hardening of the correction fluids of the present invention can Rather than due to a decrease in the shear stress during spreading. Actual A dimensionally stable, or "solid," layer that cures quickly, usually contains water, The water is then lost in the usual way, such as by evaporation.   As solidification takes place, a dimensionally stable coating can be written on or typed Or may be subject to so-called overwriting. After the liquid has spread Can be prescribed so that no delay is required or extended if necessary It can be formulated so that a delay of a few seconds or more is required. Coagulation A solid film may feel dry when touched at the same time as its formation, For liquids containing large amounts of water, the coating may initially feel slightly moist. is there. Even so, virtually immediately, surely overwrite after only a few seconds It can be performed.   Another highly preferred feature of the invention is that it solidifies without liquid loss and immediately overwrites There is a correction fluid ready to accept. Thus, in another aspect, the invention relates to aqueous Suspension medium, composite particles according to the invention, opalescent particles and a film-forming binder latex. A correction fluid, comprising: Provides a correction fluid that immediately accepts overwriting.   These highly preferred correction fluids according to the invention provide a very even distribution of the milky particles. It is usually much more evenly distributed than previously known aqueous correction fluid coatings. Provides a dimensionally stable "solid" coating that gives a much more uniform milkiness You. This is because these highly preferred liquids of the present invention comply without sacrificing milkiness. The use of thinner layers means that they can be deposited in thinner layers than It is generally advantageous in neat technology.   The method for forming a smooth and opaque coating by spreading the quick-setting correction fluid of the present invention is a heavy burden. It is important. We have found that edge shearing, such as doctor blades, knife edges, etc. Or using a Bird bar to spread the liquid and achieve instantaneous curing. Usually found to be favorable. The inventors use the term "edge shear" to support Shear stress generated in the correction fluid between the rigid straight end moving parallel to the support and the support The degree of shear stress depends on how far the edge moves away from the support and its relative movement. It depends on the speed. To spread with a brush or felt or foam spreader, It may not be enough or satisfactory to cause instantaneous cure, but a few Completely satisfactory if a delay of seconds is acceptable. Therefore, the special rapid hardening of the present invention The ionic liquid may be an edge shear member such as a knife edge spreader or a suitable It is preferably aliquoted from a container provided with other means of applying shear stress. Good In a preferred apparatus, the liquid is spread using a supply nozzle including a spreader edge. I can do it. If spread by other means, instantaneous coagulation will not be obtained, In such a case, the time before overwriting is of course longer.   As shown, the degree of shear stress is desired if the shear stress utilized is too small. This is important in that the liquid may not cure instantaneously. one In general, the optimal requirements for any liquid can be determined by routine trials and experiments. The matter becomes clear. Apply a shear stress that is easily obtained by hand on the desk That the liquid can be coagulated by the method of the present invention. It is a characteristic of the body. Generally, the degree of shear stress is from about 50 to about 10,000 s^-1Is , For example, about 2000 s.   The exact formulation of the quick-setting correction fluid of the present invention may vary depending on the nature of the ingredients. general The solids content usually exceeds 75% by weight, up to about 85% by weight or more. can do. These liquids usually provide instantaneous solidification and immediate overwrite. I can. Reduced solids content and / or reduced content of the composite particles of the invention And the overwriting time increases. Routine trials and experiments in any case Indicates the optimum condition. The amount of milky particles is usually between about 20% and 40%. You. The amount of composite material of the present invention is usually up to about 50%, more preferably 8-30. %, Most preferably 12 to 20%.   As already indicated, the preferred method of producing the quick-setting correction fluid of the present invention is a Irradiated polymerizable liquid dispersed in aqueous latex of synthetic binder is polymerized as it is. According to. In this method, a part of the film-forming binder is polymerized by the polymerizable liquid. Sometimes it is incorporated into the resulting composite material particles. This means that the film form in the final product The resulting coating should be dry, as it may cause a shortage of binder. When fragile, it tends to flake from paper and fall off. This is the irradiated correction fluid During processing, additional (unirradiated) film-forming binder is simply mixed. Can be managed. One way to do this is to use the conventional (irradiated) (Not done) is to add correction fluid latex. Therefore, the present invention The correction fluid was (a) an irradiation polymerizable liquid dispersed therein, polymerized, and (b) irradiated. Raw By mixing the product with an additional conventional (non-irradiated) aqueous correction fluid, It can be made from conventional aqueous correction fluids. Additional (unirradiated) liquid The ratio of the product of step (a) to the product of step (a) may be as high as about 90:10 by weight, Usually 50:50 to 70:30, most preferably about 60:40). . By this approach, the first product of step (a) is not only the additional film former. It can be seen that it also receives extra milky particles. This allows for a larger Covering power may have occurred.   When the composite material particles of the present invention are added to the correction fluid, the storage stability of the suspension is extremely low. It was also found to be improved. In such cases, even after several months of storage, It is not necessary to shake the container to redisperse the solids.   A feature of the present invention is that if necessary, very high solids loadings, e.g. Can be made without high viscosity. Is Rukoto. Thus, the liquid may be an unwieldy paste and / or Does not result in a stable dispersion. The liquid remains liquid, for example, 6000 Pa The viscosity may be relatively high, such as 50 s.^-1The shear stress of the bra Can be easily spread by hand with a sieve, giving a viscosity of about 300 Pas . This very high solids loading without loss of stability, etc. As such, it constitutes a further aspect of the invention. In a further aspect, the present invention provides a method comprising: (A) providing the composite material particles of the present invention; and (B) at least one compatible film-forming latex material and at least one Mixing milky particles with the material The present invention provides a method for producing a correction fluid according to the present invention.   The present invention provides a composite material particle of the present invention and an aqueous solution thereof as a component of an aqueous correction fluid. Includes the use of suspensions.   Furthermore, the present invention relates to a composite material of the present invention for forming a coating on a support. It also includes the use of filler particles or an aqueous suspension thereof.   The present invention also provides a coating on a support comprising the composite material particles of the present invention. Wherein the composite material particles are compatible with the coating in the coating. Providing a coating that is bound by the coating material.   For a more complete understanding of the present invention, FIGS. 1 to 5 are SEM pictures attached. Reference is made to the drawings.   FIG. 1 is a top view of a dried coating of Latex II correction fluid not according to the present invention.   FIG. 2 is a top view of the frozen and broken mixture described in Example 1.   FIG. 3 shows the aqueous suspension of a frozen and broken particulate material according to the invention as described in Example 1. It is a top view of a liquid.   FIG. 4 shows the dry matter produced from the aqueous suspension of the particulate material according to the invention described in Example 1. It is a top view of a dry film.   FIG. 5 is a top view of the coating of the dried correction fluid according to the invention described in Example 2. .   FIG. 6 is a diagram of a composite particle produced in the process of the present invention by polymerization of Hi-Tad (example) 1).   FIG. 7 shows Latex II (line A), aqueous suspension of particulate material according to the invention (line B) (Example 1) 5 is a chart of the particle size distribution in the correction fluid (C line) (Example 2) of the present invention.   8 (a), 8 (b) and 8 (c) show one embodiment of the correction fluid applicator of the present invention. State and its use.   Referring to the drawings, FIG. 7 shows the particle size distribution in the three liquids. The measurement was performed by Malvern Mast Performed on an ersizer apparatus, the plot shows the solid product occupied by particles of a certain diameter. % By volume. Plot A is a correction fluid not according to the present invention, the composition of which is Of latex II shown in Table 1 of FIG. As you can see (and other research Solids (film-forming latex particles and Most of the titanium particles are in the size range of 0.2-2.0 micrometers. is there. Specifically, the particle size and volume distribution are as follows.   Size range volume% 0.125 to 0.313 9.6 0.313-0.576 23.4 0.576-0.781 16.0 0.781 to 1.06 15.3 1.06 to 1.44 13.2 1.44-1.95 9.1 1.95 to 2.65 4.7 2.65 to 6.63 6.4 6.63 to 16.572.3 100.0   Particles in excess of 91% by volume are in the region of the main peak (ie, 2.65 mic in diameter). A few percent (less than 9%) of the second very small peak (e.g. That is, it exceeds 2.65 micrometers). Second peak Are believed to be primarily film-forming binder particles. further, The mode sizes of the particles at the two peaks are approximately 0.75 and 5.7, respectively. It is an icrometer.   Plot B shows an aqueous suspension of the composite (particles of the invention made in Example 1 below). (Ie, an aqueous suspension that is an irradiated mixture of Hi-Tad and Latex II) It is. As can be seen, plot B is from about 3 to about 70 micrometers. Plot A and plot A in that there is a new second peak for particles that are range sized Are significantly different. This peak is for composite material particles generated by the polymerization reaction, They also contain some filler milky particles (eg, titanium dioxide) Formation fixed to each other by a matrix of polymerized Hi-Tad The binder comprises latex particles. Particle size and volume distribution are as follows It is.   Size range volume% 0.05-0.092 2.8 0.092-0.170 6.9 0.170-0.313 10.1 0.313 to 0.576 9.9 0.576 to 1.06 7.8 1.06 to 2.65 8.1 2.65 to 3.60 1.6 3.60-9.00 6.8 9.00 to 16.57 16.3 16.57-30.53 21.8 30.53-76.327.9 100.0   The smaller size peaks (particles up to 2.65 micrometers in diameter) The larger particle size peak (2.65 micrometers) containing about 47% by volume of particles (Particles with a diameter greater than-) contain about 53% by volume of particles. In addition, two peaks The mode sizes are about 0.3 and 20 micrometers, respectively. This one A general type of bimodal size pattern is an important highly preferred feature of the present invention But why does this seem to contribute to achieving very short overwrite times? It is. This is especially true when the suspension is applied as a coating on a support. It allows small particles to occupy the interstitial space of larger particles. This effect The efficient close packing results in the almost spherical nature of the composite and latex particles. Therefore, it is made easy.   Plot C mixes the particle suspension of Plot B with Latex II (50:50) This is the correction fluid of the present invention (Example 2) thus produced. Plots B and C By comparison, the magnitude of the peak on the left is increasing (free film formation in suspension) It shows that the amount of binder particles and filler particles is increasing) , The plot retains the bimodal features of plot B. The particle size and volume distribution are as follows.Size range volume% 0.05-0.230 7.7 0.230-0.424 13.1 0.424 to 0.781 17.7 0.781 to 1.44 15.1 1.44 to 2.65 7.9 2.65 to 3.60 2.0 3.60-9.00 7.2 9.0 to 12.21 4.2 12.21 to 22.49 11.1 22.49-56.23 12.5 56.23-76.321.5 100.0   The peak on the left (diameter to about 3.60 micrometers) is about 63% by volume. Containing particles, the peak on the right (3.6 micrometers or more) is about 37% by volume of particles Including children. The mode size of the particles at the two peaks is about 0.3 and 20 micrometers.   FIG. 8 (a) illustrates one embodiment of a correction fluid applicator (80) according to the present invention. It is a schematic sectional drawing. The applicator includes a cap (83) having an outlet passage (83). 82) comprising a flexible bottle-shaped container (81) (shown inverted) with . Valves (shown) to control the ingress of air and the discharge of correction fluid from the container (81). (Not done). Within the container is the correction fluid (84) of the present invention. Content Outside the vessel (81) is a shear member (85) connected to the cap (82). The shear member (85) is shaped like a plate and has two spaced apart lower ends (87). There are leg portions (86). Between the legs (86), the retracted cutting blade (88) (See FIG. 8C).   FIGS. 8 (b) and 8 (c) show the same container as FIG. 8 (a), but in FIG. Shows the container in the direction of the sectional line AA in FIG.   In use, the applicator (80) is mounted on a support (90), for example a piece of paper. Placed in Flexible container (81) By squeezing FIG. 8 (a), one drop (91) Alternatively, a greater amount of correction fluid is drained onto the support (90). Then, The locator is tilted and carries a shear member (85) behind said drop (91). A With the applicator's legs (86) against the support (90), It is moved to the left (see arrow B in FIG. 8 (b)). A drop (91) of liquid is applied to the shear member ( 85) is spread as such a thin coating (92) by the cutting blade (88). You. During unfolding, the cutting blade (88) has subjected the liquid to edge shear. You.   1 to 6 are SEM photographs. FIG. 1 shows that the composition is not shown in Table 1 Table of coatings made with aqueous correction fluid, referred to as Latex II in this application Surface. The coating is applied by placing a drop of correction fluid on paper and applying it to 50 micrometer. It was formed by spreading it with a bird bar. The coating is made of titanium dioxide particles (1) and film-forming binder particles (2). The coating is opaque And can be bent without breaking.   2 to 6 are described in connection with Examples 1 and 2 below.   In the example, the overwrite time was measured as follows. Using a ballpoint pen, Handwritten above. A correction fluid was applied to the handwriting and the time was recorded. Of the measured interval Then, the correction liquid was overwritten and corrected by handwriting with a ballpoint pen. Overwriting If not accepted, test at longer intervals until overrides are accepted Repeated. By the word "acceptable", the inventors have determined that the correction fluid This means handwritten indicia without scratching or breaking the surface. Up The shortest interval at which the writing was accepted is recorded as the overwrite time. Ball used The pen is Papermate Flexgrip Ultra Medium, but other ballpoint pens Good.   The following examples are given for illustrative purposes only. Weight unless otherwise noted Part is used.Example 1   Place Hi-Tad liquid monomer (40 parts) in a container and add Latex II (60 parts) to it. I got it. The two components are then stirred vigorously using a dispermat mixer. Was. A sample of the mixture thus formed was frozen, crushed and shown in FIG. 2 of the accompanying drawings. Observed by SEM. Hi-Tad monomer becomes spherical spheres dispersed in the aqueous layer It is clear from FIG. Rather, Hi-Tad is a thin plate or bread It is present in a cake-like independent volume (4). These volumes are coated Surrounded by an aqueous suspension (5) containing binder particles and titanium dioxide particles Have been.   The liquid mixture sample is tightly opened on a polyethylene tube, and a total of 2 Mrad of electron beam is applied. Irradiation (in 1 Mrad increments at room temperature). Including the composite material particles of the present invention The resulting liquid, which is an aqueous suspension, has a very high viscosity (50,000 mPa.s).   s), it was stable in that no solids precipitated. Freeze the liquid sample It was crushed, crushed, and observed by SEM as shown in FIG. 3 of the accompanying drawings. Figure 3 shows the polymerization 2 shows a part of two composite particles generated by the method. These composite particles are It has film-forming binder particles on its surface. Some coating between composite particles (3) Aqueous layer containing the forming binder particles (2) and some titanium dioxide particles ( 6).   FIG. 6 shows, on a larger scale, the composite particles after separation from the liquid. composite The material particles are bound by the Hi-Tad polymer matrix (8), The film-forming binder particles (2) fixed to the matrix. The steel also contains titanium dioxide particles (1). The entire composite material particles are usually It has a diameter 50 to 100 times that of the film-forming binder particles (2). The coating forming bar The indica particles (2) are present in the composite particles and near the surface thereof (7). Coating The forming binder particles (2) and the milky particles are very close, adjacent particles are in contact And thus are connected to each other. Irradiated polymer matrix (8 ) Fills the gaps between the particles.   After irradiation, a drop of liquid was transferred from the tube to the paper and a 50 micrometer bar Expanded using a dover. The liquid is immediately smooth and relatively solid (dimensionally A (stable) opaque coating formed on the paper. The coating touches And it was dry and could write on it immediately. But the coating Had little cohesiveness and was brittle and easily removed from the paper. Coating sample S Observed by EM and photographed (FIG. 4). With reference to FIG. The composite particles (3) and the titanium dioxide particles (1). Free film formation bi Almost no under particles.   Table 1 shows the composition and properties of Latex II and the irradiated mixture.(1) Titanium dioxide commercially available from DuPont (Wilmington, Del., USA) It contains 94% titanium dioxide and about 4.5% alumina and has a particle size of 9%. 0% exceeds 0.6 micrometers, 80% exceeds 0.4 micrometers You. (2) Meta available from NYCO Minerals Inc. (Virusbro, NY, USA) Acicular particles of calcium silicate. (3) more than 97% kaolin clay and 0.35% sodium polyacryle Extender containing a soot / soda ash dispersant. Dry Branch Kaoline Co. -Drive Lunch, Gia). (4) methyl methacrylate, butyl acrylate, styrene, methacrylic acid and Synthetic acrylate / styrene polymer of 2-hydroxyethyl acrylate Tex emulsion (62% solids). Tg = 9 ° C., Union Carbide (rice (Kary, NC). (5) Synthetic acrylates of butyl acrylate, styrene and methacrylic acid Styrene polymer latex emulsion (48% solids). Union Carbide (Rice (Kary, NC). (6) Commercially available from Henkel Corp. (Ambler, PA, USA) Sodium salt of ruboxylate polymer electrolyte. (7) commercially available from Henkel Corp. (Ambler, PA, USA) Mixture of mineral oil derivative and silica antifoam. (8) Carbon black. (9) Cationic non-film forming acrylic polymer bleed inhibitor. Rohm & Haas (US Commercially available from the state of Pennsylvania). (10) Bisphenol A propyl dimethacrylate.Example 2   The irradiated liquid (50 parts) of Example 1 was replaced with a compatible film-forming layer such as Latex II. Mix with Tex liquid (50 parts) and apply one drop of the resulting correction liquid mixture to paper. Spreading the correction fluid with a 50 micrometer bird bar immediately cures and dimensionally A relatively solid coating was formed on the paper that was stable to heat. The coating has excellent milkiness and And had good flexibility and could accept overwriting immediately. SEM sample And photographed (FIG. 5). FIG. 5 is a table of the coating made from the correction fluid of the present invention. Plane. The remarkably large particles (3) are composite material particles formed by polymerization. is there. These composite particles and titanium dioxide particles (1) are They are connected to each other by the dust particles (2). Uniform particle distribution is the same as close packing. It is clear.   The inventors have found that in the correction fluid of the present invention, the composite particles, the opacifier and the Undersized particles were found to be very well dispersed. This is very high Shear stress (200,000s^-1Surprisingly, the dispersion collapses It is proved from the fact that it does not form Hofman bodies expected . Well dispersed particles, bimodal particle size distribution, composite particles and coatings Since the formed binder particles are generally spherical, the effect of shear stress from a bird bar is Fruit (about 2000s^-1) Efficiently causes close packing of the particles, thus (free and And the rate at which both (adjacent) film-forming particles on the composite particle surface coalesce and cure faster Form a relatively solid film.   Table 2 shows the composition and properties of the correction fluid. Examples 3-6   Example 1 was repeated changing the ratio of Latex II and Hi-Tad. 50:50 (Example 3) In, the irradiated product was a solid. 52:48 (Latex II: Hi-Tad) (Example 4) The product is a liquid with properties very similar to the irradiated product of Example 1. Was. Increasing the ratio of Latex II reduces the viscosity of the resulting liquid, making it easier It expands, but is dimensionally stabilized (solidified) as soon as it is subjected to shear stress. It is. Beyond about 70:30 (Example 5), the overwrite time began to increase. The composition and properties of the formulations are shown in Table 3. Examples 7 to 10   Example 2 was repeated, varying the ratio of irradiated liquid and Hi-Tad. Increase the amount of Latex II to about 80:20 ratio (Latex II: irradiated liquid) And a satisfactory correction fluid was obtained (Example 9). Increasing the amount of Latex II causes the liquid to shear. When the shear stress is applied, it is dimensionally stable enough to apparently harden into a solid. The quality is soft and tends to take a few seconds to accept overwriting. Set of compounds The composition and properties are shown in Table 4.   In these examples, increasing the percentage of Latex II expanded it using a bird bar. Because the coating has reduced thickness, it overwrites the coating very quickly, but the milky white To a lesser degree. Therefore, a fair comparison of overwrite time versus composition is not possible. Was. Therefore, the data of the overwriting time in the table was measured by different techniques. The amendment Using a brush, apply the liquid to the mark on the test sheet. Until the correction could be overwritten. For comparison, The overwrite time of the latex II measured in this way was 26 seconds. 50s^-1In Of the latex II was 52 mPa s. Examples 11 and 12   Example 1 was repeated using Latex A instead of Latex II. Latex A is non-bleed Sex correction fluid. The results obtained were basically the same as in Example 1. Therefore Irradiated product is very viscous (> 50,000 mPa) but stable liquid Met. Spread a certain amount of correction fluid using a 50 micrometer bird bar. The liquid immediately turns into a smooth, dimensionally stable, solid, opaque coating. Converted and could be overwritten immediately. Then, the liquid sample was further It was mixed with xA at a weight ratio of 50:50 (Example 11). The resulting liquid is 50 micrometer Can be expanded with a bird bar of the A coating was formed. The coating immediately accepted the overwrite.   Table 5 shows the composition and properties of Latex A and the formulation. (1) High Point Chemical Corp. (High Point, North Carolina, USA) Aliphatic quaternary dispersant for sale. (2) Commercially available from Worlee Chemie GmbH (Hamburg, Germany). (3) Diethylene dioxide commercially available from DuPont (Wilmington, Del., USA) Tan. (4) Dioxide dioxide commercially available from DuPont (Wilmington, Del., USA) Tan. (5) Vinyl acetate homopolymer emulsion (6) Amorphous silicon commercially available from Henkel Corp. (Ambler, PA, USA) Mineral oil mixed with mosquito defoamer. (7) Auraspe commercially available from Engelhard Corp. (Iselin, NJ, USA) rse carbon black W-107. (8) Bisphenol A propyl dimethacrylate.Example 13   Place Latex II (60 parts) in a container and gently use a Dispermat mixer. While stirring the mixture, the Hi-Tad monomer (40 parts) was added slowly. Finished adding After that, the resulting mixture was vigorously stirred using a Dispermat. Liquid mixing The sample was sealed in a polyethylene tube and irradiated with 2 MRad electron beam at room temperature. Was. The resulting viscous liquid behaved similarly to Example 1. Place a drop of the liquid on paper When spread using a 50 micrometer bird bar, the liquid becomes smooth and A dimensionally stable solid opaque coating was immediately formed on the paper. Said The coating was dry to the touch and could be immediately overwritten. But, The coating had little cohesion and was brittle and easily peeled from the paper. Said When the liquid was diluted with an equal volume of Latex II, a liquid with the same performance as in Example 2 was obtained. Was. One drop of the resulting liquid is applied to paper and using a 50 micrometer bird bar Upon spreading, the liquid hardened and immediately formed a solid film on the paper. The coating Has excellent milkiness and good flexibility and can accept overwriting immediately Came.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, L S, MW, SD, SZ, UG, ZW), EA (AM, AZ , BY, KG, KZ, MD, RU, TJ, TM), AL , AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, E E, ES, FI, GB, GE, GH, GM, GW, HU , ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, M D, MG, MK, MN, MW, MX, NO, NZ, PL , PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, V N, YU, ZW (72) Inventor Frederick, Charles, Baines             Bedfordshire, England, Dance             Table, Eaton, Bray, Yeah, Tu             Lee, closed, 14

Claims (1)

[Claims]   1. A substance used in liquids, A plurality of film-forming binder particles, and Polymerized polymeric material containing a portion of the film forming binder particles Comprising   The composite material, wherein the part of the binder particles is formed together with the polymerized polymer material. Material particles, The binder, wherein the composite material particles are contained in the composite material particles during polymerization. The particles are fixed to each other, such that the composite particles have a substantially spherical outer surface and about 0.5 mm. Having a diameter of 1 to about 100 micrometers, wherein some of the binder particles are A substance bound near the outer surface of the composite material particles.   2. Each of the composite material particles is coated with the above-mentioned polymerized material. Further comprising at least one opalescent particle fixed to the indder particles. Item 7. The substance according to Item 1.   3. The polymerized polymer material is polyacrylate or polymethacrylate. 2. The substance of claim 1, comprising a salt.   4. The polymer substance is bisphenol A propyl dimethacrylate, Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate And tetraethylene glycol dimethacrylate 4. The substance according to claim 3, which is derived from a polymer.   5. The film-forming binder particles are vinyl alcohol copolymer, acrylic Polymer, styrene copolymer, polyurethane and ethylene vinyl acetate A water-insoluble polymer selected from the group consisting of copolymers Item 7. The substance according to Item 1.   6. A particle comprising at least two different film forming binder particles. 2. The substance according to 1.   7. Comprising a film-forming binder having a glass transition temperature of less than 12 ° C. 2. The substance of claim 1, comprising particles.   8. A method of producing a substance for use in an aqueous correction fluid, the method comprising: Providing film-forming binder particles, Providing a polymerizable liquid, Mixing the polymerizable liquid and the film-forming binder particles, and Polymerizing the polymerizable liquid to form a composite particle suspension Comprising   Each composite material includes a portion of the film-forming binder particles, The polymeric material of the composite material particles contacts the binder particles and the binder Particles are fixed to each other, and a part of the film-forming binder particles is About 0.1 to 100 micrometer Method with the diameter of the tar.   9. 9. The method of claim 8, wherein the polymerizable liquid polymerizes upon irradiation.   10. Wherein the polymerizable liquid comprises acrylate or methacrylate, The method according to claim 8.   11. The acrylate or methacrylate is bisphenol A propyl Rudimethacrylate, ethylene glycol dimethacrylate, triethylene glycol From coal dimethacrylate or tetraethylene glycol dimethacrylate 11. The method of claim 10, wherein the method is derived from a polymer selected from the group consisting of:   12. The film-forming binder is a vinyl alcohol copolymer, acrylic Polymer, styrene copolymer, polyurethane and ethylene vinyl acetate Claims: 1. A water-insoluble polymer selected from the group consisting of copolymers. 9. The method according to 8.   13. The aqueous latex comprises at least two different film-forming binders 9. The method of claim 8, comprising particles of:   14． A film form in which the aqueous latex has a glass transition temperature of less than 17 ° C. 9. The method of claim 8, comprising particles comprising a synthetic binder.   15. The dispersion is irradiated by electron beam irradiation at a dose of 1 to 10 MRad The method of claim 9, wherein   16. The dispersion is irradiated by electron beam irradiation at a dose of 1-2 MRad The method according to claim 15,   17． The dispersion may contain up to 50% by weight of the polymerizable liquid. 9. The method according to 8.   18. 9. The method of claim 8, wherein said aqueous dispersion further comprises opacified particles.   19. An aqueous suspension for use in an aqueous correction fluid comprising the following components: (A) the substance claimed in claim 1, and (B) an aqueous suspension medium.   20. An aqueous correction fluid comprising the following components: (A) comprising particles comprising a film-forming binder suspended in an aqueous medium Aqueous latex, (B) milky particles suspended in the aqueous medium, and (C) A substance as claimed in claim 1 suspended in said aqueous medium.   21. The film-forming binder particles in the aqueous latex are contained in the substance. 21. The correction fluid according to claim 20, which is the same as the film-forming binder particles.   22. 21. The modification of claim 20, having a total solids content of at least 75% by weight. liquid.   23. 21. The correction fluid according to claim 20, comprising 10 to 50% by weight of said substance. .   24. 21. The composition according to claim 20, comprising at least 20% by weight of said milky particles. Correction fluid.   25. 21. The repair of claim 20, wherein the overwriting time of the correction fluid is less than 30 seconds. Solution.   26. 26. The repair of claim 25, wherein the overwriting time of the correction fluid is less than 15 seconds. Solution.   27. A method for producing a correction fluid, comprising the following steps. (A) A polymerizable liquid is added to an aqueous correction liquid containing particles comprising a film-forming binder. Disperse, (B) polymerizing the polymerizable liquid to form an aqueous suspension of composite material particles; The body material contacts some of the film-forming binder particles and places them relative to each other. Fixing to form the composite particles; and (C) adding the aqueous suspension to a further correction fluid.   28. 28. The method of claim 27, wherein the polymerizable liquid polymerizes upon irradiation.   29. The amount of additional correction fluid used in step (c) and the water produced in step (b) 28. The method according to claim 27, wherein the volume ratio of the aqueous suspension is from 50:50 to 90:10. Law.   30. The further correction fluid of step (c) is the same as the correction fluid used in step (a) 28. The method of claim 27, wherein   31. A method for producing a correction fluid, comprising the following steps. (A) providing the material claimed in claim 1; (B) combining said substance with at least one compatible film-forming latex material; And at least one opacifier particle.   32. Correction fluid container, outlet and dispensing for dispensing correction fluid from the container Integrated with the applicator for spreading the crushed liquid while applying shear stress. A correction fluid applicator comprising an edge shear member.   33. The edge shear member spreads the dispensed liquid while applying shear stress. 33. The app of claim 32, comprising a plate including a recessed edge for shaving. Cater.   34. A method of coating the surface with an aqueous correction fluid, Comprising particles of at least one film-forming binder suspended in an aqueous suspension medium. Aqueous latex, milky particles suspended in the aqueous medium and suspended in the aqueous medium A correction fluid comprising the substance claimed in claim 1 which is turbid, wherein said correction fluid is provided. Applying to the surface.   35. The coating spreads the liquid as a coating on the support. 35. The method of claim 34, comprising:   36. The correction fluid is spread over the surface under shear. 34. The method of claim 33.   37. 37. The method of claim 36, wherein the correction fluid is spread using edge shear. Law.   38. The edge shearing is performed by a doctor blade, knife edge or bird bar. 38. The method of claim 37, provided by a computer.   39. The composite material particles comprising the substance claimed in claim 1, wherein the composite material particles are compatible with each other. Bonded together in the coating by a reactive film-forming latex material There is a coating on the support.   40. 40. The coat of claim 39, covering at least one mark on the surface. Wing.   41. An aqueous correction fluid comprising the following components: water, Opacifier, and Film-forming binder particles and polymeric material containing the film-forming binder particles Composite particles containing.   42. The composite particles allow easy close packing in the coating composed of the correction fluid. 2. The correction fluid of claim 1, which promotes.   43. 43. The correction fluid of claim 42, wherein said composite particles are substantially spherical.   44. The composite particle has an average diameter of less than 50 micrometers. 42. The correction fluid according to claim 41.   45. A method for covering a mark on a support, comprising: water and a film-forming binder. -Composite particles containing particles and a polymeric substance containing the film-forming binder particles. Applying a correction fluid comprising the correction fluid onto the mark.