JPS6031864B2 - Non-stick tangible objects made from polymer latex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-stick tangible object made from a normally sticky elastomer and to a method for making the same.

It is a well known method to emulsify a polymerizable monomer in water and then convert it into a dispersed form of polymer. The resulting dispersion is called latex. Natural rubber is also produced in latex form. Certain latexes are very useful in their raw form, examples being base compositions for latex paints. Other applications require agglomerating the polymer and separating it from the latex. The most important commercial form of such polymers are non-stick tangible objects that are left washed and dried. The tangible object may be washed to a water-soluble monster content of less than about 3 weight percent and dried to a volatile material content of less than about 1 weight percent. If the aggregated polymer is not inherently sticky, it is easily isolated from the aqueous phase, and washing and drying yields a free-flowing powder that is easy to handle in subsequent processing steps. .

However, if the polymer is inherently sticky, the coagulation of the latex will produce an agglomerated block of polymer that is not only difficult to clean to remove impurities, but also dissolves and mixing with the material of
It is also difficult to prepare for each operation of kneading, curing, and molding. In the natural and synthetic rubber field, much attention has been paid to the problem of agglomeration of polymers that are sticky in their normal state before curing.

Several viable solutions have also been seen and proposed. In U.S. Patent No. 2,879,173, Y
The liquid was stirred for about 120 minutes until the droplets were completely frozen and agglomerated.
A method of flocculating polychloroprene latex by holding is shown below.

After separating the resulting coarse pellets, while still frozen, they are coated with an inert powder such as 5-2% by weight talc so that they do not stick together even after thawing and drying. . However, the adoption of this method is limited by the disadvantages of the cost of organic liquid recovery, the energy cost of refrigeration, and the high contamination rate of inert materials. It comes from an elastomer that is sticky under normal conditions. Washing
There remains a need for a more practical and economical method of manufacturing dried, non-stick tangible objects. In U.S. Pat. No. 3,053,824, Heim teaches flowing a latex buffered with a phosphate or borate buffer into an aqueous aluminum or titanium salt solution containing an alkali metal or alkali metal salt. The agglomeration method is shown.

This patent states that the resulting agglomerated particles do not stick together until washed to remove the coagulant salt. However, there is no description regarding the stickiness of the particles after washing. In U.S. Pat. No. 3,846,365, Bergli et al. emulsified a dilute solution of an elastomer in a volatile organic solvent with a fine solid filler for the elastomer and produced It shows a powdered filled polymer prepared by pouring the polymer into an aqueous alkali silicate solution having a pH of preferably 7 to 12 and evaporating the organic solvent. A fine non-stick coprecipitate of latex and silicic acid residue forms. It is stated that condensation of silicate anions should be avoided. The present invention is based on the discovery that washed, dried, non-stick, uncured elastomeric tangible objects can be produced from normally sticky elastomeric latex in a simple and inexpensive manner.

The present invention contains less than about 3% by weight of water-soluble materials and less than about 1% by weight of volatile materials, based on the total weight of the shaped object;
about 0.05 to 3% by weight of a monolithic porous coating of a water-insoluble hydrous inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. have Made of uncured elastomer that is sticky under normal conditions, with a minimum dimension of approximately 0.
．． To provide non-stick elastomer tangible objects of 01 to 10 legs. The term "integral" means that the coating is cohesive, rather than being composed of discrete particles as is the case with powder coatings.

"Minimum dimension" means the diameter of the smallest circular hole through which the tangible object can pass vertically. A unique feature of the present invention is that the non-stick tangible object is highly porous prior to removal of water-soluble and volatile substances.

This porosity is evidenced by the object's opaque appearance when dispersed in water and by the porous structure of its cross-section in a microscopic view. Due to this porosity, hydrolysates and volatile substances are easily removed by washing and drying operations, respectively. Some of the porous structure still remains after washing and drying. The non-stick elastomer tangible object of the present invention is a tangible object made from a normally sticky uncured elastomer latex having a solids content of 20 to 65% by weight, based on the total weight of [a} about 0.5 to 25% by weight of a soluble salt that has an agglomerating effect on the latex; and about 0.01 to 5% by weight of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and It contains a soluble or colloidally dispersed hydrous inorganic oxide selected from the group consisting of a mixture of 1. The NaOHI droplet is brought into contact with an aqueous solution that is within the range of about 2 to 7 mL so that when dropped, the droplet is immediately surrounded by a cloudy coating of gelled hydrous inorganic oxide, thereby coagulating the latex. The elastomer is manufactured by a process comprising producing a highly porous body of agglomerated elastomer coated with a water-insoluble inorganic oxide.

The tangible object is then washed with water to a water content of about 3% by weight of free-flowing substances and dried to a content of volatile substances of less than about 1% by weight, thereby rendering it free-flowing. It can be made into a non-stick elastomeric tangible object. The invention is particularly suitable for producing non-stick pellets of uncured neoprene. The term "tangible" is used herein to refer to the latex before contact with the aqueous material; the term "tangible" refers to the latex and subsequent elastomer after the material enters the case. used to refer to. In the present invention, a coating of an inorganic oxide polymer is chemically deposited from a solution or dispersion liquid in an aqueous bath onto a normally sticky elastomeric tangible object.

Thus, in its as-produced state, the coating is a porous, non-particulate, integral film that completely surrounds each tangible object. For the integrity of the coating, the amount of coating material incorporated (
A non-sticky object can be obtained with very little loading. This is particularly important for elastomers that are subsequently melted and then cured, and also for elastomers that undergo granular (powder) such as talc, which are traditionally used to make uncured elastomer bodies non-stick. This is in sharp contrast to the high levels of contamination required for materials such as The product of the invention is a non-stick tangible object of uncured elastomer that is sticky under normal conditions.

The term "elastomer" is well known to those skilled in the art and has already been defined in publications such as the American ASTM Glossary for Rubber and Rubber-Like Materials page. "Elastomer" means an elastomer that, when uncured and in its most crystalline state, two pieces stick together at room temperature. Elastomers suitable for use in the present invention include homopolymers and copolymers of conjugated genes such as neoprene and natural rubber; copolymers of conjugated genes with other polymerizable organic monomers, such as butadiene-acrylonitrile and butadiene-styrene copolymers. : Elastomeric fluoropolymers (fluorine-containing polymers), preferably copolymers of vinylidene fluoride and at least one other fluorine-containing monomer, such as vinylidene fluoride-hexafluoropyrobene copolymers (U.S. Pat. No. 3,051,
No. 677), and tetrafluoroethylene-vinylidene fluoride-hexafluoroproventer polymers (U.S. Pat. No. 2,968,649); adhesive-type elastomers such as polyvinyl acetate and ethylene-vinyl acetate copolymers: acrylics. Includes materials such as acrylate rubbers such as acid lower alkyl ester polymers; hydrocarbon elastomers such as polyisobutylene, ethylene-propylene-nonconjugated hydrogen turborimers;

A preferred elastomer is neoprene.

"Neoprene" means an elastomer consisting of at least about 50% chloroprene (2-1,3-butadiene). Typical copolymers that can be used for chloroprene include vinyl aromatic compounds such as styrene, vinyltoluenes and vinylnaphthalenes, pan-aliphatic conjugated diolefin compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl- 1,3-butadiene, and 2,3-dichloro-1,3-butadiene: vinyl ethers, esters and ketones, such as methyl vinyl ether, vinyl acetate, and methyl vinyl ketone; esters of acrylic and methacrylic acid,
amides and nitriles such as ethyl acrylate,
Methyl methacrylate, methacrylamide and acrylonitrile: etc. The neoprene latex used in the present invention can be made by the known aqueous emulsion polymerization of chloroprene using a sodium rosinate dispersant and a free radical polymerization catalyst (eg, potassium persulfate).

Sodium rosinate dispersants can be prepared in situ from rosin acid and sodium hydroxide. Additives such as fillers, antioxidants, etc. may also be present during the polymerization.

After the polymerization has proceeded to a desired degree of completion, a catalyst stopper may be added and the remaining chloroprene removed by stripping. Minor variations in this reaction procedure yield polymer latexes that vary in molecular weight, viscosity, degree of crystallinity, and other properties. For forming pellets in the process of the present invention, the solids content of the latex should be at least about 2% by weight. Suitable latexes have a solids content of up to about 65%.
Generally, when the solids content exceeds about 65%, the latex will coagulate. Preferably, the fixed content of the latex is about 35-50%. The present invention describes the process of adding a normally sticky elastomeric latex to an aqueous agglomerate/coating matrix in a nub, controlled flow, or some other form of dispensing, thereby forming a coated tangible object. include. The latex emulsion must be stable so that it remains an emulsion during this process until the flocculating salt and, if present, the neutralizing agent have sufficiently penetrated the tangible object. Early coalescence (coalesc)
In order to prevent eMe), neoprene latex is generally stabilized with sodium rosinate and natural rubber is stabilized with ammonia. Aqueous flocculants and coatings contain latex flocculant salts, ie, salts that act to flocculate the elastomer latex. Suitable flocculant salts are well known to those skilled in the art and are described, for example, in J. C. "Neoprene Latex" by Carl
See pl.9-21, published by DuPont. Useful salts that can be used include the water-soluble sulfates, chlorides, bromides, nitrates of ammonium, sodium, potassium, calcium, magnesium, strontium, barium, lithium, beryllium, aluminum, manganese, zinc, yttrium, iron and gadmium. , citrate, acetate, formate and phosphate. Mixtures of such salts can also be used. Desirable (but not essential) characteristics of flocculant salts are low cost, colorless solution, cations and anions cannot be easily oxidized or reduced, and no alkali metal salts accumulate in the bath. It is non-toxic and does not pollute the environment.

Preferably, the salt is chemically inert to, and preferably inert to, the elastomer. Preferred salts are the soluble chlorides, sulfates of sodium, potassium, ammonium, calcium, magnesium and aluminum;
They are acetate, nitrate, nitrate and phosphate. The most preferred salts are the soluble chlorides and sulfates of the above cations. The flocculant salt may represent about 0.5-25% by weight of the case. The range of effective amounts of flocculant salts in this range in each case will vary depending on the pH of the latex type and the type of inorganic oxide present. Generally, the optimal and preferred amount of salt is in the range of about 1-10%. The bath further contains a soluble or colloidally dispersed hydrous inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. These oxides are generally thought to exist in polymerized form, and their structures can be linear chains, ribbons, or, if highly cross-linked, globular, and are similar to those of inorganic elements. The atoms are arranged alternating with oxygen atoms. In such polymers,
Some of the terminal groups are -OH groups. Inorganic oxides may also be used in water-soluble form, as in the case of polysilicic acids and polyaluminates, or as described in U.S. Pat. No. 2,574,9
It can also be used in more highly polymerized particulate forms, such as in the case of colloidally dispersible silica sols as described in No. 02 and colloidally dispersible alumina sols as described in No. 2,590,833. It can be done.

In fact, most aqueous systems containing such compounds contain polymeric oxides, at least in part, in the form of dispersed particles. The terms "silicic acid polymer" and "alumic acid polymer" are intended to encompass both soluble and colloidally dispersible forms of the polymer. The inorganic oxide may be crystalline or amorphous, and mixtures of two or more such oxides may also be used. The most preferred inorganic oxides are polysilicic acid, polyaluminic acid and silicic acid-aluminic acid copolymers. If the flocculant salt used is an aluminum salt and the inorganic oxide is a polysilicic acid, some of the aluminate hydroxyl groups formed on the alkaline surface of the latex will copolymerize by condensation with the silanol groups to form an aluminate-silicic acid. Acid copolymers may be formed. If the flocculant salt used is not an aluminum salt, especially when the case utilizes polysilicic acid as the coating material, it is typically about 0.002 to
Adding 2% by weight of ionizable aluminum salt is
Not required, but desirable. Copolymerization of aluminum has not been demonstrated, but this could explain why the inorganic oxide becomes more effective as a coating, perhaps by reducing the solubility of the coating in subsequent wash water. It has been found that yttrium salts are also equivalent to aluminum salts for this purpose and may be partially or completely replaced. Therefore, the term "silicic acid-alumic acid copolymer" should be construed to include this equivalent substitution. It is generally accepted that in freshly prepared silicic acid solutions, silicic acid is not monomeric and has a molecular weight on the order of about 1000.

As the silicic acid solution ages (changes over time), the molecular weight continues to increase, and eventually the solution gels (Bech, J. Ph. Chem-59, 532-541, 1).
(see 955). The silicic acid solution used in the present invention has a gel time of about 90% before being added to the silicic acid solution.
It is better to use one that has not been aged for a longer time than 0%.
Preferably, the silicic acid solution has been aged for about 5-70% of its gel time before being added to the bath. In continuous operation, silicic acid is continuously added to the cage and removed simultaneously. In that case, the average maturity of the borislicic acid reaches a constant value that is smaller than its gelation time. The hydrous inorganic oxide is approximately 0.01 to 5% by weight of the aggregates.
can account for. The presence of more than about 5% inorganic oxides does not lead to any further improvement in the sticky properties of the product. Preferably, the inorganic oxide is present in an amount of about 0.03-2% by weight. Oxides may polymerize or crystallize during the coating operation. One criterion for determining when a cast is no longer suitable for the method of the invention is agglomeration of the cast due to changes in conditions such as pH or depletion of essential components. Optionally, a small amount of surface surfactant may also be included to reduce air-liquid interfacial tension and aid in penetration of the latex material into the cage.

Suitable surface surfactants are effective at low concentrations, compatible (i.e., do not cause polymerization or crosslinking of the hydrous oxide components), and are inert toward flocculant salts. It is. A wide range of nonionic, anionic,
Cationic and amphoteric surfactants can be used. Examples of suitable surfactants include lower alkyl alcohols such as ethanol, trimethyl nonanol ether of ethylene oxide, sodium hebutadecyl sulfate, sodium lauryl sulfate, condensation-based products of tertiary niamine and ethylene oxide, fluorinated amphoteric There are surfactants, etc. The surfactant lowers the air-liquid interfacial tension to about 5M skin e/
Preferably, it is added in an amount sufficient to reduce the skin density to less than 100%, especially less than about 39 skin e/skin. It can be used in a pH range of about 2-7.

When the pH is below about 2, inorganic oxides are less likely to gel on the surface of a tangible object. When the pH is above about 7, inorganic oxides may convert to soluble salts. The usable pH range within this range for a particular system will vary depending on the type of latex, flocculant salt and inorganic oxides present. Within this range, pH values of about 2.5 to 5.5 are particularly preferred for an optimal balance between case stabilization and coating effectiveness. As the alkaline latex material enters the bath, maintaining the scale within a predetermined range by adding appropriate neutralizing agents can substantially increase the life of the scale. organic or inorganic acids, such as acetic acid,
Hydrolyzable acid salts such as aqueous hydrochloric acid and AsoCso3 are particularly preferred neutralizing agents. The effectiveness of coatings on tangible objects depends on the amount and type of hydrous inorganic oxides present;
and the pH of the case.

It has been found that not all combinations of the above variables result in effective baths. Although the requirements for vulgarity to function are not fully understood, a simple test has been discovered to determine whether cases function. This test consists of 1. State N
Only one drop of aOH is added to the container. The case is functional when the droplet is immediately surrounded by a cloudy coating of gelled hydrous oxide. Although the pH of various latexes varies over a wide range, it is preferred that the pH of the latex is the same as or higher than the pH of the grade.

If the latex is neoprene containing sodium rosinate as a stabilizer, the pH of the latex will be greater than about 7 unless acidified. When dropping latex, the resulting congealed tangible objects may be lumps, beads, pellets, etc., depending on the surface tension and density of the condensing case and its speed and direction as the latex enters the case. (with or without), disc-shaped, or ring-shaped.

When latex is added as a controlled stream, filamentary flow results in condensed fibers or continuous beads (gading); flat or curved flow spreads result in condensation, bongs, sheets, or tubes. do.

Both drip and controlled flow can be applied either above or below the surface. Most preferably, the latex is added dropwise onto the surface of the rack. When the latex is placed in the bath and the condensed coating material moves within the case, the case is provided with a certain degree of porgy. If desired, additional rope means in the form of agitation or agitation may be introduced to help maintain bath uniformity. As mentioned above, when the pH level is maintained by adding an acid, the Haji group is particularly desirable. The process of the present invention can be carried out at temperatures ranging from about 0 to 10 degrees centigrade.

Temperatures in the range of about 5 to 70 qo are preferred, and about 10 to 40 qo
The range of 0.degree. C. is particularly preferred due to the excellent stability in this range. Pressure is not a critical factor in the method of the invention, and any pressure above or below atmospheric pressure can be used.

Atmospheric pressure is preferred for convenience. The time from when an elastomeric latex body enters the bath until a non-stick elastomeric body is removed from it varies widely, depending in part on the smallest dimensions of the body to be coated.

This time ranges from about 0.5 seconds to about 6 hours or more. Upon contact with the bath, the latex will immediately form a cohesive, non-stick coating (e.g. approximately 0.5%,
(within 5 seconds) on the surface of the agglomerated tangible object. If it is desired that the latex coagulation and neutralization be completed to the center of the coated object before it is removed from the bath, a longer retention time of the coated object in the bath is employed. In preferred cases, this may be less than about 6 minutes. Since the flocculant that has soaked into the tangible object continues to migrate toward the center of the object even after the object is removed from the container, complete flocculation in the container is not an essential requirement. However, it is preferred to leave the object in the bath until sufficient flocculant has soaked into the object to complete the flocculation. Referring now to the drawings, FIG. 1 depicts one preferred embodiment of apparatus suitable for carrying out the method of the present invention. This device consists of a cylindrical tank 11 (inner diameter 27
．． The tank 11 includes a cylindrical draft pipe 12 (inner diameter 12.7 mm) coaxial with the tank 11. The tube and tank may be constructed of any rigid material such as glass, metal or plastic. At the tip of the upper end of the draft pipe 12,
A wire mesh screen 13 whose mesh dimensions are smaller than the dimensions of the tangible object to be manufactured is connected. The liquid 14 containing the inorganic oxide polymer and the flocculant salt is held at a level such that the bath surface 15 is slightly below the top of the screen 13. Polymer latex droplets or discontinuities are introduced into the chamber within a zone delimited by screen 13. In this embodiment, a stainless steel capillary tube 16 (1.9 mm length, 0.86 mm inner diameter, 13 mm outer diameter) is used to form the latex droplets. These tubes 16 are seated via polytetrafluoroethylene plugs to a stainless steel plate bolted to the lower end of tube 17 (inner diameter 10.1 mm). The spacing between the centers of two adjacent capillaries fixed on the plate is 1.11 skins. The 61 capillaries are arranged in a hexagonal array of 5 capillaries on each side.

The number of drops (frequency) on the tray is adjusted by changing the liquid level of the latex in the pipe 17. A path in which the flow of bath solution generally descends through the draft tube, then ascends through the space between the draft tube and the tank wall, then through the screen and back to the screened surface. In order to promote the circulation of water, a hawk pump 18 is provided at the bottom of the tank 11.

For this purpose, a 3-lobed (15 mm diameter) is used.
A 24-arc) marine propeller is used. A screen at the top of the draft tube provides a means for directing the solution containing no tangible objects into the top of the draft tube.

This screen also keeps out bubbles created by the slag, helping to keep the surface free of clumps that could affect the uniformity of the tangible objects falling therethrough. Baffles 19 (width 3.81 mm) are arranged vertically along the wall of the tank 11 at 900 mm intervals to enhance the taihai and thereby assist in the suspension of the coated latex particles in the annular space outside the draft tube. has been done. This baffle is not necessarily necessary depending on the type of Taihai you use. Through the action of draft tubes, screens, mulchers and baffles, the bodies are brought into contact with the coated particles and the fresh, bubble-free solution.

The tangible objects descend into the draft pipe in pieces. Since the physical objects are coated by the time they exit the draft pipe, the tendency for agglomeration with already coated physical objects is eliminated. The coated tangible object is then kept suspended outside the draft tube until removed from the bath. A typical batch operation using this equipment is performed as follows. First, case 1 consists of an aqueous solution of an inorganic salt, a small amount of a surfactant, and a coating material.
Prepare 4. The salt acts to coagulate the latex during and after coating. Surfactants facilitate the passage of latex droplets across common surfaces. Latex is applied to the standpipe 17 to create a predetermined head pressure and then continuously replenished with latex to maintain this head pressure on the capillary tube.

Since there is no withdrawal of solution from the bath during operation, the level of the bath rises due to latex dripping. stand pipe 1
7 and the draft pipe 12 are both mounted so as to be movable in the vertical direction. During each run, close the capillary outlet to the surface 1.
The stand pipe and draft pipe are moved so as to maintain the top of the screen 13 approximately 2.54 skin above the bath surface 15 and approximately 0.835 skin above the bath surface 15, respectively. In the loading method illustrated in the attached drawings, the coated tangible objects can only be taken out at once at the end of each operation, but in this method, a tank is used to continuously take out the coated aggregated tangible objects from the rack. 11 is provided with an overflow pipe, the suspension of tangible objects passing through the overflow pipe is filtered through the furnace, the furnace liquid is generally recirculated, and the bath components are replaced as they are consumed, thereby allowing continuous operation. It can also be implemented. A major advantage of the present invention is that large quantities of uncured tangible objects can be stored in contact with each other under normal conditions without causing agglomeration and remain free-flowing and easily disentangled. be.

The minimum dimension of the tangible object is about 0.01 to 1 inch. Minimum dimension is at least about 0.0 to avoid dusting
1 rib or more. Tangible objects whose smallest dimension is greater than about 1 m² require excessive force to mix with other ingredients in use. Preferably, the maximum dimension of the tangible object is about 0.1 to 5 cm. Since the bodies added to the bath consist of latex, the water-soluble flocculant salt readily penetrates into the aqueous phase of the bodies, thereby flocculating the latex with minimal internal coalescence.

As a result, the aggregated elastomer within the non-stick coating remains sufficiently porous for a sufficient period of time to allow washing away of water-soluble components, including flocculant salts. In the case of relatively crystalline elastomers, this porosity is maintained throughout. In the case of relatively amorphous elastomers such as neoprene, the porosity decreases when left for a long time, but does not disappear completely. After coating and agglomeration, the condensed tangible object can be separated from the case by suitable means.

After removal from the bath, it is desirable to remove water-soluble materials and volatile materials from the tangible object. To this end, in the customary manner, washing is first carried out with water or a polar organic solvent, followed by squeezing, centrifugation or drying. The tangible object may be cleaned until the content of port substances is less than about 3% by weight, preferably less than about 1%. After removing a predetermined amount of waterborne substances, the tangible object is dried to remove volatile substances. Drying may be carried out at an air temperature of about 25 to 25,000 degrees. Preferably, drying is carried out at an air temperature of about 100-13,500°C.
During this drying operation, the temperature of the tangible object is maintained below the known thermal decomposition temperature of the polymer. Drying continues until the tangible object has a volatile content of less than about 1% by weight, preferably about 0.5% by weight. During these finishing steps, relatively hard polymers (eg, due to crystallinity) remain opaque and porous, while normally sticky polymers coalesce further and become translucent. Nevertheless, even such polymers retain traces of their previous highly porous structure and retain the non-stick nature of the hydrous oxide coating deposited on their outer surfaces. This non-stick coating may be reinforced, if desired, at a later stage of the high temperature drying, for example by adding small amounts of talc. Non-stick coatings on elastomers that are sticky under normal conditions are also initially porous so that moisture, solvents, soluble reaction components and by-products are easily removed from the interior of the coated object.

The coating may represent about 0.05-3% by weight of the coated tangible object. Less than about 0.05% generally does not provide sufficient non-stick properties;
More than that usually does not provide additional benefits to offset the increased cost. Preferably, the coating is about 0.5-2% by weight of the coated article. Due to cleaning operations such as those described above, the need for both the non-stick coating and the coalesced elastomer to remain porous for some time after the formation of the tangible object is emphasized. FIG. 3 is a micrograph of a cross-section of a typical porous tangible object according to the present invention. The porosity of the tangible object is evident in this photo. The voids appear as dark areas as seen at 20. The non-stick coating appears as a pale area as easily seen at 21. The non-stick coated object of the present invention further comprises a filler,
Pigments, colorants, softeners, extenders, antioxidants, stabilizers,
It may contain a curing agent and the like.

Incorporation of such materials can be carried out by adding them either to the raw polymer latex or to the agglomerated/coated matrix. The following examples illustrate the production of non-stick elastomeric tangible objects of the present invention.

The washed and dried non-stick elastomer tangible objects produced in these examples all contained less than about 3% by weight water-soluble materials and about 1% by weight volatile materials. It was full. Also, in any case,
The inorganic oxide polymer coating accounts for about 0.05-3% by weight of the tangible object, and the smallest dimension of the tangible object is about 0.01-3% by weight of the tangible object.
It was one ship. In the examples, all parts and percentages are by weight. The neoprene latex used in the following examples was prepared as follows. Neoprene latex deck. 1 This latex was prepared from an alkaline aqueous emulsion containing 100 parts of chloroprene and 0.23 parts of dodecyl mercaptan modifier, stabilized with 2.9 parts of disproportionated wood rosin sodium salt.

The emulsion temperature was adjusted to 40°C, and 0.3% K2S was added.
Polymerization of chloroprene was carried out by continuously adding an aqueous solution containing 208 and 0.015% anthraquinone-B-sulfonic acid sodium salt at a rate such that the temperature could be controlled at 40 qo by external cooling. When the conversion rate of chloroprene monomer reached about 67%,
0.015 parts of phenothiazine and 0.015 parts of 4t
The polymerization was stopped by addition of an aqueous emulsion of toluene solution containing -butylcatechol. After distilling off the residual monomers, the latex contained approximately 37% solids.

The logarithmic viscosity of this polymer is 1.20 (0.1 m/100
Notoichi benzene, 30k0), and the pH of latex
was approximately 1.2. Neoprene latex M. An alkaline aqueous emulsion was prepared containing 10 parts of dichloroprene, 0.15 parts of dodecyl mercaptan, and 3.5 parts of the sodium salt of disproportionated Woodlodge.

Polymerization of chloroprene was carried out by adjusting the emulsion temperature to 10 pm and adding 1.0% K2S203, 0.05% anthraquinone-8-sulfonic acid sodium salt, and 0.14% anthraquinone-8-sulfonic acid sodium salt.
This was done by continuously adding an aqueous dispersion containing 10-20 qo of cumene hydroperoxide at a rate such that the temperature could be controlled. When the conversion of chloroprene monomer reached 85%, the polymerization was stopped by adding a toluene solution of 0.03 parts of phenothiazine and 0.03 parts of 4-t-butylcatechol in the form of an aqueous emulsion. Ta. After removing the residual monomers, the solids content of the emulsion was about 37% and the pH was 1.
It was 2.5.

Neoprene latex No. Instead of 10 parts of 3-chloroprene, 92 parts of chloroprene and 2.3-dichloro-1,
Using a mixture of 8 parts of 3-butadiene, neoprene latex no. The preparation method of 1 was repeated.

Polymerization was stopped at a conversion rate of 65%, and the solid content of the latex after monomer distillation was about 33% and pH' was 12. Neoprene latex M. 4. The amount of dodecyl mercaptan in the monomer emulsion was reduced to 0.12 parts instead of 0.15 parts, and a neobrene latex fabric was prepared. The method described in 2 was repeated.

The resulting latex had a solids content of 37% and a pH of 12.5. Example 1 0.29M silicic acid aqueous solution (prepared by ion-exchanging Na+ to H+ in 0.28M sodium metasilicate aqueous solution) 9
In fact, by mixing 10 parts of a 50% Ca(N03)2 aqueous solution and 100 parts of anhydrous ethanol, almost 0
．． A case containing 7% Si02 and 3.9% Ca(N03)2 was prepared.

Approximately 20' neoprene latex fabric. 1 (solid content 37
%, pH 12) was dripped into this bath through an orifice located at about 2 skin heights. The surface of the droplet aggregates upon contact,
Globules were formed which aggregated completely within a few minutes and were covered with a non-stick coating. The resulting opaque pellet was removed from the rack and dried in a 6000 oven. Even at room temperature, the pellets remained dry and still retained their soft feel and free-flowing properties. For comparison, the following experiment outside the scope of the present invention was performed.

The above example was repeated using 90% water instead of the silicic acid solution. The demulsion droplets coagulated rapidly but were very sticky and could not be broken apart after drying at 60°C. was difficult. Example 2 IM silicic acid loo0', 50% CaC SO2 solution 60', absolute ethanol 700' [and distilled water 240']
approximately 3.6% Si02 and 2.6% Ca
A case containing Cso2 was prepared.

Approximately 200 neoprene latex seams. 1 (solid content 37
%, pH 12) was added dropwise. The resulting beret was left on the rack for 30 minutes. The pellets were removed, washed with 70% ethanol, and dried for 4 hours in a vacuum drying piston heated with refluxing acetone. The obtained pellet had the following analytical values. Ca
, 0.25: Na, 0.38: Si, 0.51: Ash content,
2.8%. The pellets thus prepared retained a small amount of alkali. This amount of residual alkaline stabilizes the neoprene against HC degradation. A 5% suspension of this pellet in water had a pH of 9.0. The pellets have a solubility in toluene of over 90%, indicating that little or no crosslinking of the neoprene has occurred to date. Example 3 Using a dilute aqueous solution of a nonionic surfactant to lower the interfacial tension at the air-liquid interface to approximately 1.5
An alcohol-free case containing % SiO2 and 2.1% CaCSO2 was prepared.

Freshly prepared 0.9M silicic acid 1ow', trimethyl nona/-lether of ethylene oxide (Tergito
TM Nagi-6, Union Carbide Co.) 0.2%
The scale was made up of a mixture of 9.4 ml of aqueous solution and 20.6 ml of 50% CaC. Approximately 2 in neoprene latex M. 1 (37% solids, pH 12) was added dropwise to form an opaque, non-stick pellet.
It was isolated, washed with water, and air dried to produce free-flowing, non-stick pellets 3-4 ribs in diameter. The moisture content of pellets is 0.38%; the ash residue is 3.05%; other analytical values are Cao. 44%: Nao. 26%: Sil. 11
%Met. Example 4 o. QM silicic acid (pH 3.3) 1000 units, trimethyl nonanol ether of ethylene oxide (TergMI
■TMN-6) 0.2% aqueous solution 94 [, and 50%
From a 60% CaC2 aqueous solution and 1.6% Si0
A bath containing 2 was prepared.

The initial pH of the grade was 4.45. Neoprene latex M. 1 (fixed content 37%, pH 12) 100'
Drop it over 0 minutes and worship the character, 1.
The pH was maintained at 4.0 by continuous addition of side hydrochloric acid. Zoku showed no signs of gelling. The resulting neoprene latex was screened onto a 100 mesh stainless steel screen, washed with cold water, and dried. The product was non-sticky and free-flowing. Example 5 A silicic acid solution was prepared from a sodium silicate solution with a Si02/Na20 ratio of 1.95 as follows.

The sodium silicate solution used was grade 6 (Dupont), which had a viscosity of 60.00 specific p (Iso ℃), a specific gravity of 1.708, Na20 = 18.4%, and Si02 = 36.
It was 0. This solution (166.5 kites) was diluted 2 times with distilled water. The resulting solution was passed through an acid form intestinal ion exchange column containing a 1300 ml intestinal ion exchange resin (Rekarinol, Nichiju). The first 500' of effluent corresponding to the retention capacity of the column was discarded and the remainder was collected. 1000' of this 0.88M silicic acid solution was used in the method of Example 4 to form a case containing approximately 2.5% Si02. The nominal pH was 3.1 at the beginning of the neoprene latex addition and 4.1 at the end of the addition. The resulting pellets were washed with distilled water and dried. It showed a slight tendency to aggregate. Example 6 Approximately 1.4% Si02 and 7.6% Na from 10% NaC aqueous solution 15 and 1.0M silicic acid aqueous solution 5'
A formula containing C was prepared.

About 2' of a 55% solids latex of a copolymer derived from about 18% pinyl acetate and about 82% ethylene was added dropwise to the bath. The droplets aggregate to form pellets, which are separated from the bath in a furnace, dried under vacuum at 80 qo, washed with water, and treated with Na.
All traces of C were removed and dried again. The product was non-sticky and free-flowing. For comparison, the following experiment outside the scope of the present invention was performed.

The above experiment was repeated twice, first by replacing the NaC solution with water,
The second time, the silicic acid solution was replaced with water and the process was repeated. In both cases, the treated droplets were too fragile to be removed intact from the rack. Example 7 High speed hawking of IMNa2Si03 and bait LOIOO'
In addition, INHC〆262 secretion, NaC 14.7 evening and day 20 spot secretion, approximately 1.4% Si02 and 6.1
% of NaC was prepared.

To this solution at about 0°C was added vinyl acetate/as described in Example 6.
A latex of ethylene copolymer was added. 1
After 0 minutes, the obtained beret was removed from the rack and heated to 80qC.
It was dried in a vacuum dryer for 2 hours.

The pellets were coated with a non-stick coating and were free-flowing. Example 8 Approximately 0.0% IM silicic acid was prepared from 250% of anhydrous EtOH, 1750% of anhydrous EtOH, and 50% Ca2.60% aqueous solution.
A natural rubber latex with a solids content of 62% (La xTS
C. Approximately 200 drops of Jabei (aIL Latex) were added.

The latex hardened rapidly and a non-stick coating formed on the surface of the particles. When this pellet was taken out and dried, it was non-sticky and free-flowing. Example 9 Neoprene latex M. 1 (solid content 37%, pH 12), the necessary amount of carbon black (SPrlin Funai. Cabot Corp.) was mixed in so as to generate a uniform emulsion containing 4% carbon black based on neoprene. .

About 20% of this modified latex was treated with a 0.9M aqueous solution of silicic acid (100ml), 0.2% ethylene oxide trimethyl nonanol ether (TegMI~TMN-6) aqueous solution, and a 50% CaC〆2 aqueous solution (6M). 1 prepared from
．． It was added dropwise to a container containing 5% SiO2 and 2.1% CaCSO2. The droplet was dropped from a Pasteur pipette near the surface of the case, and the case was rinsed with a magnetic rod. After standing for approximately 3 minutes, the resulting pellet was removed by decantation, washed three times with 500 g of water, and air-dried. The resulting carbon-containing pellet was non-sticky and free-flowing. Example 10 Repeat the method of Example 9, but instead of 4% carbon black in the latex, 10
% aluminum atomization powder was used.

A non-stick, free-flowing aluminum-containing pellet was obtained. Example 11 Repeat the method of Example 9, except that 4 in latex
% carbon black instead of 10% alumina 3
Hydrate (powder, graded at 135-195 oo) was used.

A non-sticky, free-flowing alumina-containing pellet is obtained. Example 12 Repeat the method of Example 9, except that 4 in the latex
% carbon black instead of 10% magnetic iron oxide (
Fe304, MO-4232, Pfizer Miner
als Inc.) was used.

A non-sticky, free-flowing pellet containing iron oxide is obtained,
This could be easily controlled with magnets. Example 1
3 Vinylidene fluoride 45%, hexafluoropropylene 3
65% solids content of turbolimer of fluoroelastomer derived from 0% and 25% tetrafluoroethylene
Approximately 100% of the latex was saturated with BaC 20%.
．． 8 M silicic acid aqueous solution 500 ml, BaC saturated water 500 ml, and trimethyl nonanol ether of ethylene oxide (Tergtol TMN-6)
A 2% aqueous solution of 2' was added dropwise to a container prepared from 2'.

The droplets flattened on contact with the scale, but were generally agglomerated and coated with a non-stick coating. The particles were separated by decantation, washed repeatedly with water, and air dried to yield free-flowing white flakes approximately 5 mm in diameter. Example 14 Equal volume neoprene latex shame. A mixture of Example 1 (37% solids, pH 12) and the fluoroelastomer aqueous latex of Example 1 was prepared.

This mixture (20') was mixed with 10' of 0.8 M silicic acid aqueous solution.
0.0, 0.2% aqueous solution of ethylene oxide trimethyl nonanol ether (Tergen tol TMN-6) 94
and a 50% aqueous solution of CaC was added dropwise to a container containing approximately 1.5% SiO and 2.1% of CaC. The resulting pellets were washed with water and then dried first in air and then on P205 at room temperature under vacuum. The obtained mixed elastomeric polymer is not sticky,
It was easily liquid. Example 15 Sodium silicate solution (Grade F, DuPont, Si
02/Na20 ratio = 3.2fu Na20 = 87%, Si0
2 = 28.4%, viscosity (total 00) = 16 ratio p, specific gravity = 1
．． 6) 422' was diluted with distilled water.

This solution was passed through the acid form cation exchange column described in Example 5. The obtained approximately 0.6 law M silicic acid solution 25
Approximately 0.5% Si0 using 1000 g of 15% NH4C, 250 g of distilled water, and 500 g of a 0.05% aqueous solution of ethylene oxide trimethyl nonanol ether (Tergtol TMN-6) and 7
．． A bath containing 6% NH4C was prepared. Neoprene latex M. 2 (37% solids, pH 12
．． 5) Dropped 200 units. 30 generated pellets
I put it in the minute case. Decant the case,
The beret was washed three times with two portions of water each. The pellets were air dried at room temperature under atmospheric pressure. The resulting pellet is not sticky;
It was easily liquid. Example 16 A case was prepared using a buffer to withstand the pH increase associated with the addition of alkaline neoprene latex.

The buffer was 2M dichloromethane, 1.75% trimethyl nonanol ether of ethylene oxide (Tergibl T
MN-6) 0.1 and 12.60M glycine solution
A mixture was prepared by diluting 50' with distilled water. Add this buffer to 0.6 M silicic acid (prepared in Example 15).
Added to a mixture of 100' and 50' of 30% NH4C aqueous solution. Neoprene latex M. 2(
20' (37% mass, pH 12.5) was added dropwise. The pH of the bath only changed from 3.35 to 3.55 compared to a pH change of approximately 6.0 for a similar case without buffer. Approximately 80M latex could be added to this buffer solution before the pH rose above 6.0. When the pH exceeded 6.0, gelation occurred rapidly. Example 17 0.6 $M Silicic Acid (Prepared as in Example 15) 10
00%, 30% NH4C, 500' and ethylene oxide trimethyl nonanol ether (Terg blood 1
From a 500M 0.2% aqueous solution of TMN-6), approximately 2.
A case containing 0% SiO2 and 7.9% NFC was prepared.

Shame on neoprene latex. 3 (33% solids, state 12)
200' was adjusted from pH 12 to pH 12.5 by addition of INNaOH. This latex was dropped into the above-mentioned rack. The resulting pellets were washed with water and then freeze-dried under high vacuum at about 17,800 ml. At room temperature, the dried pellets were non-stick and free-flowing. Example 18 A powder was prepared using an alumina-modified silica sol (Ludox 13M, DuPont).

This product is a 30% solids acidic aqueous dispersion of positively charged colloidal particles consisting of a dense silica core coated with positively charged polymeric alumina. The approximate chemical composition is Si02 = 26%, Aso203 = 4.0%,
C: 1.4%, Mg0=0.2%, viscosity (25
°C) = 5-1&p, pH (250o) = 4.3-4. Particle size = 16m, specific gravity (25qo) = 1.2
It is 3. 0.2% aqueous solution of sodium heptadecyl sulfate anionic surfactant (Tergi ionic 7, Union Carbide Co., Ltd.) 116, 15
A solution containing approximately 0.7% SjQ/A and 6.1% NH4C was prepared from an aqueous solution of 80% NH4C and the above alumina-modified silica sol 4. In this bath, neoprene latex M. 2 (solid content 37
%, pH 12.5) was added dropwise. The droplets agglomerated and the resulting coated pellets were washed and dried. A non-sticky, free-flowing pellet was obtained. Example 19 0.69M silicic acid (prepared as in Example 15) 5',
30%A SoC 3 Group 20/Aqueous solution 9', ethylene oxide trimethyl nonanol ether (TergMI■T
Approximately 1.0% Si02 and 8.0% AtaC from a 0.2% aqueous solution of MN-6) 5' and distilled water 1'
A case containing part 3 was prepared.

Neoprene latex M. 2 (37% solids,
pH 12.5) 2' was added dropwise. The droplets coagulated and were removed from the rack, washed, and dried. A non-sticky, free-flowing pellet was obtained. Examples 20-23, respectively 0.6 M of silicic acid aqueous solution (prepared as in Example 15), 2.5 M of ethylene oxide trimethyl nonanol ether (Tergi's 1 TMNI-6);
5% aqueous solution 5% and 30% aqueous solution 12.5 of the following salts:
I prepared four types of slang from [.

Example 20 N Br Example 21 (N is) 2HC6 public 07 (citrate) Example 22 (N is) 2Cr207 Example 23
NASCN Neoprene latex M. 2 (solid content 37%, pH 12.5) was added dropwise.

The produced elastomer pellets were separately washed with water and dried. A non-sticky, free-flowing pellet was produced. Example 24 Naphthene-based extender (Sumex 79uS
Neoprene latex M.U.I.L.) 10' 2(
90' (37% solids, pH 12.5) and the mixture was shaken vigorously to form an emulsion.

0.6M silicic acid aqueous solution (prepared as in Example 15)5
0', 15% N ratio C, 100% aqueous solution and ethylene oxide trimethyl/nanol ether (Tergi)
A case containing approximately 1.0% Si02 and 7.6% NAC was prepared from 50 volumes of a 0.05% aqueous solution of 1.TMN-6).

The oil-stretched polymer latex described above was added dropwise to this bath. The resulting pellet was removed from the bath, washed with water, and dried to yield a non-stick, free-flowing pellet of oil-stripped elastomer. Example 25 100 ml of NaC was dissolved in 900 ml of 0.39M silicic acid aqueous solution, and 100 ml of NaC was dissolved in ethylene oxide trimethyl nonanol ether (Tergtol TMN-
Dissolve 900 ml of 0.05% aqueous solution of 6) and combine both solutions to obtain approximately 0.9% Si02 and 10.0% NaC.
A case containing 〆 was prepared.

Neopre Solatex M. 2 (37% solids, pH 12
．． 5) During the dropwise addition of 200ml, the pH was maintained at 4-4.5 by the addition of INHC. 1 for the generated bullet
The pellet was left to stand for a period of time, then washed with water and dried to obtain a non-stick, free-flowing, uncured elastomer pellet. Example 26 0. 25' of dissolved silicic acid (prepared as in Example 15),
Ethylene oxide trimethyl nonanol ether (Te
A 10% solution of 30% NH4C dissolved in a 0.2% aqueous solution of rgtolTMN-6), ethylene oxide trimethyl nonanol ether (TergtoITMN-6)
6) 20% NaC solution dissolved in 0.2% aqueous solution 4
0 and 125' of distilled water to approx.
3% Si02, 3.9% NH4C and 11.1
A bath containing % of NaC was prepared.

This case was adjusted to pH 5.0 with INNaOH. Neoprene latex M. 2 (fixed content 37%, pH 12.5)
20M was added dropwise, and INHC was simultaneously added dropwise to maintain the pH at 5.0. The resulting pellet was separated from the bath after 1 hour, washed three times with 500 g of distilled water, and air-dried to yield a non-stick, free-flowing pellet. Example 27 Approximately 0.5% chlorhydrol (AZ20347.
Aluminum chlorohydroxide polymer type complex containing 0% and 16.3% chlorine, Reheis Chemica
1) and 2.3% CaC〆2.
% chlorohydrol aqueous solution, ethylene oxide trimethyl nonanol ether (TergtolTMN)
-6) 0.05% aqueous solution 175% and 25% Ca
It was prepared by mixing two aqueous solutions 15 times.

The solution was brought to pH 5.0 with INNaOH. Neoprene latex No. 2 (37% solids, pH 12.5)
While dropping 20 '
A pH of 5.0 was maintained by the addition. The pellets were left in the bath for 1 hour and then washed three times with 250ml of distilled water. When the pellets were storm dried, free-flowing, non-stick elastomeric particles were formed. Example
28 0.6 rule M silicic acid (prepared as in Example 15) 100
A surfactant-free solution containing 1.0% Sj02 and 7.6% NH4C was prepared from 15% N ratio C200, and distilled water 100%.

I filled 100' graduated cylinders with this slang.

Neoprene latex M.200 from a 10' syringe with a 20 gauge needle. 2 (37% solids, pH 12.5) is extruded in a continuous flow from one side of the graduated cylinder onto a common surface to form a 4. puddle.

When the tip of the paddle was picked up with tweezers from the opposite side of the graduated cylinder, continuous fibers of polychloroprene coated with aggregated hydrated silica were pulled out. After washing and air drying, the fibers were not sticky. Example 29 The method of Example 28 was repeated, but more force was used on the syringe so that the latex flow penetrated the surface of the case.

The weight of the condensing stream dragged the latex to the bottom of the bath, where it collected non-stick continuous fibers of elastomer about 1-2 skins in diameter. Example 30 Repeat the method of Example 29, but after the latex flow penetrates the bath surface interface, reduce the pressure on the syringe so that the separated vial falls from the needle into the bath. It was adjusted.

The resulting pellets were non-stick and free-flowing after washing and drying. Example 31 A: Axis 8.6 to 9.3 damaged in blender
To 200% aqueous colloidal sol (Ludox AM, DuPont) of 30% solids of alumina-modified silica was added 2.0% concentrated hydrochloric acid.

The resulting colloidal solution had a solids content of approximately 29%;
The pH was 3.0. B: Neoprene latex M.
2 (solids content 37%, pH 12.5)
,000, Union Carbide Co.) 1% aqueous solution 10
A modified neoprene latex was prepared by adding '.

This emulsion is kept in a vacuum to prevent creaming. C: 2.5% of the colloidal silica solution prepared in A above, 10.0% of the 15% NH4C aqueous solution, an amphoteric fluorinated surfactant (nyl
■ Mix 1 part of a 0.2% aqueous solution of FSB (DuPont) and 6.5 parts of water to obtain approximately 4.3% Si02/A.
A sample containing 203 and 7.5% of N-C was prepared.

Approximately 5 ml of the modified neoprene latex prepared in B above was added dropwise to this container. The resulting pellets were separated from the bath, washed with water, and dried to yield non-stick, free-flowing, substantially spherical pellets of modified neoprene. Example 32 0.6 rule M silicic acid aqueous solution (prepared as in Example 15)
250M, 15% N ratio C, aqueous solution 1000', water 20
A 0.05% aqueous solution of trimethyl nonanol ether of ethylene oxide (TergtolTMN-6) and 1% ASOCZ3.8LO, which had been adjusted to pH 50 by adding INNaOH, were added.
Mix 50' of aqueous solution with approximately 0.5% Si02
, 7.6% NH4C and 0.01% ASoC3
A case containing .

After that, neobrene latex M. 2 (37% solids,
pH 12.5) 200 secretion was dripped over 8 minutes,
For the next 1 hour this bath is heated to 50% by addition of INHC.
was held at The aggregated droplets were separated from the bath, washed with water three times, and soaked in water for 3 hours, then air-dried. The resulting pellet was non-sticky and free-flowing. Example 33 INHC evening? In a solution of 0 secretion dissolved in 595' of water,
15% aqueous silica sol (N col■2) under intense flocculation.
15, N col, pHI. 05) 265' was added to prepare a silica sol with approximately 4.6% solids and pH of 5.0.

The above sol 250', a 15% aqueous NAC solution loo0', a 0.03% aqueous solution 700' of an amphoteric fluorinated surfactant (Nyl FSB, DuPont), and the pH was adjusted to 5.0 with INNaOH in advance. 1% A kept
Mix 50 parts of the mother LO aqueous solution to approximately 0
．． 6% Si02, 7.6% NH4C and 0.0
A bath containing 13% AC was prepared. The obtained case was 4.3. Shame on neoprene latex. 2(
This condition was observed during the dropwise addition of 200 ml (fixed content: 37%, pH 12.5), and the addition of HC increased the pH to 4.
It was maintained at 5-5.0. The generated pellet is 1 in the world.
He was worshiped for hours, separated from the world, washed three times with water, and immersed in water twice. After drying, the pellets were not sticky and showed little tendency to agglomeration. Example 34 A 49% solids aqueous colloidal silica sol (Ludox™, DuPont, pH 8.0) was prepared as in Example 33.
9, Particle size 220-250A)
．． 5.6% S
An aqueous sol containing i02 was formed.

In place of the sol used in Example 33, the above sol 250' was used, containing approximately 0.7% Si02, 7.6% NH4C and 0.013% ASO3. A solution was prepared and the pH was maintained at 5.0 by the addition of INHC. Other treatments were the same as in Example 33,
A non-sticky, free-flowing elastomer pellet was obtained. Example 35 A 30% solids aqueous colloidal silica sol (Ludox SM
, pH 9.9, DuPont)
[and water 637'].

The above Sol 250 secretion was used in place of the sol used in Example 33, and the other treatments were the same as in Example 33.
A non-sticky, free-flowing pellet was obtained. Example
36 30% solids aqueous colloidal sol of alumina-modified silica with a pH of approximately 8.9 (Ludox Yama M, DuPont) 4
00' was added with concentrated hydrochloric acid (38%) 4.0 ml while stirring vigorously.

The resulting sol had a pH of 3.0 and a solids content of about 29.
It was 7%. From 250% of this sol, 1000% of a 15% aqueous solution of NH4C, 650% of water and 100% of a 0.2% aqueous solution of an amphoteric fluorinated surfactant (Renyl FSB, DuPont), approximately 4.3 % Si02 and 7.5% NH4C was prepared. The pH of this case is 3.7, and the neoprene latex M. 2(
Fixed content 37%, pH 12.5) 0 while dropping 200 secretions
．． The pH was kept below 4.5 by the addition of 1N HC. The droplets agglomerated, but were then allowed to stand in the bath for 30 minutes, separated from the bath, washed three times with water, and dried at 60°C to obtain a non-stick pellet. Example 37 0.69M aqueous silicic acid solution (prepared as in Example 15) 1
On a desk, mix a 0.2% ethanol solution of ethylene oxide trimethyl nonanol ether (Tergtol™ dish-6) and a 50% CaC2.2LO aqueous solution of approximately 1.5% Si02. and 7.
A bath containing 6% CaC So2.20 was prepared.

In this case, a butadiene/acrylonitrile copolymer latex with a solids content of 40% (Chemi
x550, Goodyear, pH 8.0) was added dropwise to leLa. The agglomerated droplets were allowed to stand for 1 hour in a sauna, then separated from the bath and dried under vacuum at 60:00 to yield free-flowing, non-stick, perfectly spherical pellets. Example 38 Neoprene latex shame. 2 (37% solids, FH12
．． 5) A mixed latex was prepared from 100' and natural rubber latex TSC (solid content 62%, Neraltex Co., Ltd.) 60'.

The resulting mixture was brought to pH 12.0 by addition of INNaOH.
I made it 2. The scale was prepared as in Example 37, but the scale was increased by one step. While dropping the mixed latex into the bath, the rating was maintained at -5.0 by the addition of INHC. The agglomerated droplets were kept in the cage for 1 hour. It was then removed from the rack, washed three times with water and dried first in air for 5 hours and then on P24 under vacuum at room temperature for 3 days. The neoprene rubber coated pellets obtained were non-sticky and free-flowing. Example 39 Silica sol modified with positively charged alumina (Ludox■13 mountain M, Example 18) 40', 15
%N ratio C aqueous solution 100 and 0.05% sodium lauryl sulfate aqueous solution (Duponol WA
QE, DuPont) 960' and mixed with approximately 0.
A case containing 7% Si02/Aso203 and 7.6% NH4C was prepared.

The pH of the neoprene latex M. 2 (solid content 37%, pH 12.5) INH even during dropping of 200M
The pH was maintained at 5.0 by addition of CZ. The agglomerated droplets were allowed to stand in a bath for one hour, rinsed with water, and storm dried to yield a non-stick, free-flowing pellet. Example 40 15% N ratio C〆 aqueous solution loo0, 0.1% sodium lauryl sulfate aqueous solution (Duponol WAQ
E) 980M and chlorhydrol (Aso2C347
．． 0%, chlorine 16.3%. Reheis Chemica
lCO. ) was mixed to prepare a case containing approximately 0.1% chlorohydrol and 7.6% NH4C.

Neoprene latex M. 4 was added dropwise for 200 minutes, during which time the pH was maintained at pH 5.5 by the addition of INHC. After addition, the berets were lit in a cage for 1 hour, washed with water, and air-dried. This final cured elastomer pellet was non-stick and free-flowing. Example 41 Using the apparatus illustrated in FIGS. 1 and 2, the following aqueous solutions were mixed in tank 1.

15% ammonium chloride aqueous solution 10,000 secretion 0
．． 03% sodium lauryl sulfate surfactant aqueous solution (Duponol WAQE)
9,500' colloidal alumina-modified silica sol (Ludox 130M, Example 1) with a solids content of 30%.
8) The grade thus prepared had a pH of 5.4 and approximately 0.9% Si02.
It contained 7.6% of NAC.

While performing deep worship, neoprene latex M. 40% solids neoprene latex 348 prepared by method 2.
The mixture was dripped from a capillary tube over a period of 13 minutes. At the same time, add 51 IN hydrochloric acid little by little to bring the pH to 5.
．． It was kept at 4. After 13 minutes of latex dripping time,
Incubation was continued for an additional 17 minutes without further addition of acid.

During that time the pH of the bath rose to 6.6. These 17 particles
It was maintained in a suspended/floating state with a lily pad for a holding time of 10 minutes.
Thereafter, the coagulator was stopped, the particles were allowed to settle, and the supernatant liquid was separated from the particles by decantation. 8000 nails'
After adding distilled water, the particles were rinsed for 5 minutes to wash the particles.

Thereafter, the thickener was stopped and the liquid was separated from the particles by decantation. This washing operation was repeated twice. The particles were air dried to a constant weight of 1315 mm. The product was free-flowing and non-sticky. Example 42 Using the apparatus illustrated in FIGS. 1 and 2, a case was prepared by mixing the following aqueous solutions in tank 1.

15% ammonium chloride aqueous solution 10,000 [
0.03% sodium lauryl sulfate surfactant aqueous solution (DupoMI WAQE) Aqueous colloidal silica sol modified with 9,950-yield polyaluminic acid
The above modified silica sol was converted into an aqueous colloidal silica sol (Ludox M, DuPont, Si02 = 30%, average particle size = 7m, SiQ/Na20, weight ratio = 50, pH at 2530) in a blender.
A 35% aqueous solution of basic aluminum acetate stabilized with boric acid (Niapr
The mixture was prepared by slowly adding 500 g of the powder (Union Carbide Co., Ltd.) and heating the mixture with coarse oven paper to remove a small amount of gel.

The scale thus prepared has a pH of 5.3 and approximately 0.01%
It contained a colloidal silica sol coated with polyaluminic acid and an N ratio of 7.6%. While doing the rope azusa, neobrane latex M. Neoprene latex 3590 with a solids content of 40% prepared in the same manner as in Example 1 was dripped into the case from a capillary tube over a period of 9 minutes.

During this addition the pH of the case rose to 6.7. The lights were continued for an additional 51 minutes while keeping the particles in suspension, during which time no appreciable pH change occurred. The Isoazusa machine was stopped, the particles were allowed to settle, and the supernatant liquid was separated from the particles by decantation. The particles were washed by adding 8,000 ml of distilled water and rinsing for 10 minutes.

Thereafter, the Takaazusa machine was stopped, and the supernatant liquid was separated from the particles by decantation. This washing operation was repeated three times.
The particles were air dried to a constant weight of 1446 mm. The product was free-flowing and non-sticky. Example 43 The following aqueous solutions were mixed in tank 1 using the apparatus illustrated in FIGS. 1 and 2.

15% ammonium chloride aqueous solution 10,000'
0.03% Sodium lauryl sulfate surfactant aqueous solution (Dupo blood 1 WAQE) 9,950 pieces Polyaluminic acid modified aqueous colloidal silica sol as described in Example 4
was 5.2.

Neoprene latex M. 40% solids neoprene latex 45 prepared similarly to 2.
78 minutes was dripped from the capillary tube over 18 minutes. During that time the pH rose to 6.7. Rinsing continued for an additional 42 minutes, keeping the particles in suspension, during which time there was no appreciable change in pH. The Takayo machine was stopped, the particles were allowed to settle, and the supernatant liquid was separated from the particles by decantation. The particles were washed by adding 20,000 ml of distilled water and incubating for 10 minutes.

Thereafter, a filter was taken and the supernatant liquid was separated from the particles by dicantation. This washing operation was repeated once more. The particles were air dried to a constant weight of 1767 mm.
The product was free-flowing and non-sticky. Example 44 Wednesday 1694 evening, A So C So 3, Mother LOIO. 0 evening, CaC
Evening 2 - General 2024.2 evening, NaC 12.0 evening, amphoteric fluorinated surfactant (INYL FSB, DuPont)
pH 1.2 and pH 2.2 containing 4.8% Si02.
0.0 colloidal silica sol 250' is mixed with approximately 0.6% SiO2, 0.9% CaCSO2, 0.
A case containing 3% ASO3 and 0.6% NaC was prepared.

The colloidal silica sol used above was an aqueous silica sol (Ludox Thick M, DuPont) 12 with a solid content of 30%.
A mixture of 5' and water 125' was poured onto water 637 and I
It was prepared by adding it to a running blender containing NHC Yu40. In this case, neoprene latex M. 40% solids prepared in the same manner as 1.
A patch of neoprene latex was dripped onto the desk.

After three millings, the bath was separated from the resulting pellet by decantation.

The pellets were soaked in the water for 30 minutes, separated from the wash and placed in a basket centrifuge for 2 minutes. Thereafter, the pellet was mixed with talcum powder in an amount of 1.5% of its own weight, spread on a tray, and air-dried overnight. Thereafter, it was further vacuum dried on P205 at room temperature. The resultant non-stick, free-flowing pellet was determined by non-aqueous titration with the end point determined using bromphal.
．． It contained 58 heq (milliequivalents) of residual alkalinity. Example 45 Wednesday 1714.6 evening, A so C evening 3, Mother's Day 2010.0 evening,
On the evening of April 4th, 2024, trimethyl nonanol ether of ethylene oxide (Tergitol T
MN-6) 1.2 nights and 5 days of aging.
Mix 6 ml of silicic acid with approximately 0.5% SiO2, 0.9% CaC〆2, and 0.3% A
A case containing SoCso3 was prepared.

Neoprene latex material for this case. 200' of neoprene latex with a solids content of 40% prepared in the same manner as in 1 was added dropwise. The resulting pellets were removed, washed, and dried in the same manner as in Example 44. The resulting free-flowing, non-stick pellet had a residual alkalinity of 2.43 heq/100 heq. Example 46 Above the sodium silicate solution 2 described in Example 15, INN
aOH15 top and neoprene latex M. A latex mixture was prepared from one puff of neoprene latex with a solids content of 40% prepared in the same manner as in Example 2.

Water 898. Physically, 2% A so C so 3, 8 LO (INNaO
Adjusted to pH 3.5 with H) 1000 secretion, anhydrous Ca
C 236.4 evening, NaC 34 evening, 30% sodium lauryl sulfate (Duponol WAQE) 1
．． The modified aqueous colloidal silica sol 30 described in Example 4 was prepared from approximately 1.8% CaC, 1.7% NaC, 0.6% AC and 0 The above latex mixture was added dropwise to a container containing .6% modified sol. The pellets produced as described in Example 44 were removed from the cage after one meal, washed with water, dehydrated in a deep D, treated with talc, and dried. The resulting pellet was non-sticky and free-flowing.

[Brief explanation of the drawing]

FIG. 1 is a central vertical section and partial side view of a preferred apparatus for carrying out one embodiment of the method of the present invention. FIG. 2 is a top view of the same device as FIG. 1 taken along line 2-2. FIG. 3 is a micrograph of a cross section of a porous tangible object according to the invention. 11... Cylindrical tank, 12... Draft pipe, 13... Screen, 14... Bath, 16
... Capillary tube, 17 ... Stand pipe, 18.
...Rope Azusa machine, 20...Gap, 21...
・Non-stick coating. f16.1FiG. 2 fiG. 3

Claims (1)

[Scope of Claims] 1. Contains less than 3% by weight of water-soluble substances and less than 1% by weight of volatile substances, based on the total weight of the molded object, and contains from 0.05 to 3% by weight of volatile substances.
sticky in its normal state, having an integral porous coating of a water-insoluble hydrous inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof in the amount by weight A non-stick elastomeric tangible object consisting of an uncured elastomer and having a minimum dimension of 0.01 to 10 mm. 2. A tangible object according to claim 1, wherein the elastomer is neoprene. 3. A tangible object according to claim 2, in which the coating is 0.5 to 2% by weight of the tangible object, and the tangible object contains less than 1% by weight of a water-soluble substance and less than 0.5% by weight of a volatile substance. and the minimum dimension of the tangible object is 0.1 to 5 mm. 4. The tangible object according to claim 3, wherein the inorganic oxide is a silicic acid polymer. 5. A tangible object according to claim 4 in the form of a neoprene fiber having a silicic acid polymer coating. 6. The tangible object according to claim 3, wherein the inorganic oxide is an aluminate polymer. 7. The tangible object according to claim 1, wherein the elastomer is a fluoropolymer and an inorganic oxide silicic acid polymer. 8. Normally having an integral porous coating of 0.05 to 3% by weight of a water-insoluble hydrous inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. Made of uncured elastomer that is sticky in the state of , the minimum dimension is 0.01
~10 mm, a highly porous non-stick elastomeric tangible object whose high degree of porosity is demonstrated by an opaque appearance when dispersed in water and a cross-section with a porous structure on a microscopic view. 9. The tangible object of claim 8, wherein the elastomer is neoprene and the inorganic oxide is a silicic acid polymer. 10. The tangible object of claim 9, which contains less than 3% by weight of water-soluble substances and less than 1% by weight of volatile substances. 11 The tangible object according to claim 10, wherein the coating is 0.5 to 2% by weight of the tangible object, and the tangible object is 1% by weight.
Contains less than 0.5% by weight of water-soluble substances and less than 0.5% by weight of volatile substances, and the smallest dimension of the tangible object is between 0.1 and 5 mm. 12. Shaped bodies of normally sticky uncured elastomeric latex having a solids content of 20 to 65% by weight, based on the total weight of the bath, (a) 0.5 to 25% by weight of said latex; (b) a soluble salt having an aggregating action;
0.01 to 5% by weight of a soluble or colloidally dispersed hydrous inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. contact with an aqueous bath containing a pH of 2 to 7 such that when a drop of 1.0N NaOH is added to the bath, the droplet is immediately surrounded by a hazy coating of gelled hydrous inorganic oxide. to cause the latex to coagulate,
1. A process for producing non-stick elastomeric objects, characterized in that they produce highly porous aggregated elastomeric objects coated with water-insoluble hydrous inorganic oxides. 13. The method of claim 12, wherein the elastomer is neoprene. 14. The method of claim 13, wherein the inorganic oxide is soluble. 15. The method of claim 14, wherein the inorganic oxide is a polysilicic acid that has not been aged for more than 90% of its gel time before being added to the bath. 16. The method of claim 13, wherein the latex has a solids content of 35 to 50% and the latex is dropped onto the surface of a bath having a pH of 2.5 to 5.5. 17. The method according to claim 16, wherein the bath comprises:
0.002-2% by weight of an ionizable salt of a metal selected from the group consisting of aluminum and yttrium 0.0
0.03-2% by weight of an inorganic oxide. 18. The method of claim 17, wherein the inorganic oxide is soluble. 19. The method of claim 18, wherein the inorganic oxide is added to the bath for 5 to 70 hours of its gel time.
% time aged polysilicic acid method. 20 The method according to claim 12, wherein the highly porous tangible object obtained is washed with water until the content of water-soluble substances is less than 3% by weight, and the content of volatile substances is reduced to A method of forming free-flowing, non-stick elastomeric tangible objects by drying to less than 1% by weight. 21. The method of claim 20, wherein the elastomer is neoprene and the polysilicic acid has not been aged for more than 90% of its gel time before the inorganic oxide is added to the bath. A certain way. 22. The method of claim 21, wherein the latex has a solids content of 35 to 50% and is dropped onto the surface of a bath having a pH of 2.5 to 5.5. 23. The method according to claim 22, wherein the bath comprises:
1 to 10% by weight of a flocculating salt, including 0.002 to 2% by weight of an ionizable salt of a metal selected from the group consisting of aluminum and yttrium, and 5% of its gel time before being added to the bath. 0.03-2% by weight of polysilicic acid which had been aged for ~70% of the time. 24
The method of claim 23, wherein the washing step reduces the content of water-soluble substances to less than 1% by weight, and the drying step reduces the content of volatile substances to less than 0.5% by weight. How to do it. 25 (a) 0.5 to 2 % of a soluble salt that has an agglomerating effect on the uncured elastomer latex, which is sticky under normal conditions.
5% by weight, and (b) 0.01 to 0.01 to 0.01% to 0.01% to 0.01 to 0.5% of a soluble or colloidally dispersed hydrous inorganic oxide selected from the group consisting of silicic acid polymers, aluminic acid polymers, silicic acid-aluminic acid copolymers, and mixtures thereof. 5% by weight, and at a pH between 2 and 7 such that when one drop of 1.0N NaOH is added to the bath, the droplet is immediately surrounded by a hazy coating of hydrous inorganic oxide that gels. Coating bath with flocculating action within range. 26 The bath according to claim 25, which comprises (a)
1 to 10% by weight of a cohesive salt, including 0.002 to 2% by weight of an ionizable salt of a metal selected from the group consisting of aluminum and yttrium; and (b) 0 inorganic oxides.
．． 03 to 2% by weight, and the pH of the bath is 2.5 to 5.
．． Something that is 5. 27. The bath according to claim 26, in which the inorganic oxide is soluble. 28. The bath according to claim 27, wherein the inorganic oxide is polysilicic acid. 29. The bath according to claim 26, which is a sol in which an inorganic oxide can be dispersed in colloidal form. 30. The bath according to claim 29, wherein the colloidally dispersible sol is a silica sol. 31. The bath of claim 28 further comprising a compatible surfactant sufficient to reduce the air-liquid interfacial tension to less than 50 dyne/cm.