JPH04506371A - Water resistant polymer emulsion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Water resistant polymer emulsion jL The present invention relates to water-resistant polymer emulsions and methods of making polymer emulsions.

Oil-based products are present to render the surface of the substrate water resistant. but, Due to increasing environmental constraints on oil-based products, these products The long-term effectiveness of is questionable.

Also plate-shaped! h The present invention relates to a water-based polymer emulsion used to make the surface of a substrate water resistant. Provide liquid. The polymer emulsion contains at least about 40% solids and (i ) Polymer containing (ii) water and (ij) a surfactant. Usually this emulsion has a surface active content of less than about 1% by weight based on the total weight of monomers in the polymer. Contains an agent. The polymer contains from about 25 to about 90% by weight soft monomer, from about 10 to about 75% by weight of hard monomers, about 1 to about 5% by weight of olefinic carboxylic acid monomers and and from about 0.5% to about 5% by weight of crosslinking monomer. Description and claims The term "soft monomer" used in Taste: "Hard monomer" means a monomer whose homopolymer Tg is higher than about 30°C. : "Weight% of hard monomer" "Weight% of soft monomer" "Olefinic carvone "wt% of acid monomer" and "wt% of crosslinking monomer" are respectively The total dry weight of each constituent component used in the production of the polymer is It means dividing by the total weight of the monomers used and multiplying this quotient by 100%. general The emulsion has a surface tension of at least about 45 dyn/cm and the polymer The average particle size of is less than 250 oaI.

When applied to a surface and dried, the emulsion forms a water-resistant film.

The invention also includes a method of making this emulsion. This method consists of (a) soft polymers, hard monomers, olefinic carboxylic acids, crosslinkers and additional catalysts. (b) delay adding L/L to form an emulsion; Immediately after the end of the addition step, the pH of the emulsion is adjusted to remove all the carboxylic acids in the polymer. It consists of a step of substantially neutralizing the groups and stabilizing the emulsion. "Delayed addition" is during polymerization. A technical term that refers to adding ingredients at least part of the time.

Main dish Ω■ Hoseiku Hada In the present invention, each polymer emulsion consists of (i) a polymer, (ii) water, and (ii) an interface. Contains surfactant. Generally, the emulsion contains less than about 1% by weight surfactant. As used herein and in the claims, "% by weight of surfactant" refers to The total dry weight of the surfactants used in making the polymer is Divide by the total weight of monomers and multiply this quotient by 100%. Preferably, The emulsion contains less than about 0.5% surfactant.

In general, when all other parameters are held constant, the amount of surfactant in the polymer is As the content decreases, the polymer becomes less sensitive to water and the surface tension of the emulsion decreases. Power increases. Typically, the emulsion has a surface tension of at least about 45 dyn/c-A. and preferably about 45 to about 65 dyn/am.

This surfactant is typically a copolymerizable surfactant, an anionic surfactant, or a non-ionic surfactant. It is an onic surfactant or a mixture of two or more of these surfactants. representative Copolymerizable surfactants include sulfoethyl methacrylate, vinyl sulfone acid salt, sulfopropyl methacrylate, styrene sulfonate, 2-acrylic acid including, but not limited to, mido-2-methylsulfonate and mixtures thereof; Not done. Anionic surfactants include alkylphenol ethoxylate surfactants. Phates and sulfonates, alkyl sulfates and sulfonates and Non-ionic surfactants, including but not limited to mixtures thereof, include: Alkylaryl polyether alcohol, alkylphenol ethoxylate , alkyl ethoxylate, ethylene oxide/propylene oxide block Including, but not limited to, copolymers and mixtures thereof.

The polymer generally contains from about 25 to about 90% by weight soft monomer, from about 10 to about 75% by weight. of hard monomers, about 1 to about 5% by weight of olefinic carboxylic acids, and about 0.5 to about It consists of 5% by weight crosslinking agent and typically has a Tg of about -50 to about 50°C. good Preferably, the polymer contains about 2% to about 4% by weight olefinic carboxylic acid and about 1% by weight olefinic carboxylic acid and about 1% by weight. Contains ~3% by weight crosslinking agent.

Olefinic carboxylic acid monomers are monoolefinic carboxylic acid monomers and di- Contains olefinic carboxylic acid monomers.

Typical monoolefinic carboxylic acids include acrylic acid and methacrylic acid but are not limited to these. Representative diolefinic carboxylic acids include itaconic acid. It is. A preferred olefinic carboxylic acid monomer is methacrylic acid. but , mixtures of olefinic carboxylic acids can also be used.

Typical crosslinking agents are N-methylol acrylamide and N-methylol methacrylate. Amide, diacrylate, dimethacrylate, triallyl cyanurate, diaryl Lumaleate, methyl acrylamide glycolate methyl ether, formula I (formula R, is selected from the group consisting of hydrogen atoms and halogen atoms, and R1 is water. selected from the group consisting of elementary atoms, halo, thio and monovalent organic groups, R1 is a divalent group, Z is selected from the group consisting of an organic acyl group and a cyano group; This includes olefinically unsaturated monomers represented by Preferably, R3 is a hydrogen atom, and R2 is a hydrogen atom or an alkyl group having up to about 10 carbon atoms, and R3 is an alkyl group having up to about 40 carbon atoms. Z is a cyclic or acyclic organic group having an atom, and Z is represented by the following formula (in which R4 is a hydrogen atom) and monovalent organic groups) is a group. More preferably, R3 is a selected group having up to about 20 carbon atoms. an acyclic group of up to about 6 carbon atoms in length, with any and all side groups each having up to about 6 carbon atoms. R4 is a hydrogen atom or up to about 7 carbon atoms. It is an alkyl group having a child. R.

is most preferably an alkylene group having up to about 10 carbon atoms; is most preferably a methyl group. For commercial availability, the formula I A preferred crosslinking agent is acetoacetoxyethyl methacrylate. However, the most Another preferred crosslinking agent is N-methylolacrylamide.

In one example of the invention, the emulsion is made of synthetic board (or particle board) or Used as a water-resistant edge sealant for plywood.

In this example, the weight ratio of hard monomers to soft monomers in the polymer is from about 1=1 to about 1 5:1 and the polymer preferably has a Tg of about 0 to about 20°C. Typical First, in this example of the invention, the emulsion is applied to a substrate at ambient temperature and allowed to dry.

However, in a second embodiment of the invention, the emulsion is heated at elevated temperatures, such as above about 50°C. It is applied to a substrate, for example a ceramic or cement tile, and dried. child In the second example, the weight ratio of hard monomers to soft monomers in the polymer is preferably is about 1.5=1 to about 3:1, and the polymer preferably has a Tg of about 30 to about 50°. It is C.

In other examples, the emulsion is used as a water-resistant pressure sensitive adhesive (PSA). After this In one example, the weight ratio of hard monomers to soft monomers in the polymer is preferably about 1. =4 to about 1:9, and the polymer preferably has a Tg of about -35 to about -50°C. Ru.

In all examples of the invention, the soft and hard monomers typically make up the total amount of the polymer. (constituting at least about 90% by weight, preferably at least about 95% by weight of the polymer) .

The soft monomer is typically a non-functional acrylic monomers selected from the group consisting of ethylene, and mixtures thereof. Specification As used in the claims, "non-functional monomer" refers to a monomer that is further reacted after polymerization. Any group that may undergo reaction, such as hydroxyl group, carboxyl group, amide and a monomer having no amine; "soft monomer" means a homopolymer T Refers to monomers where g is less than about -20°C. Non-functional acrylic monomers are preferred. It is a desirable soft monomer.

The non-functional acrylic monomer has the following formula■ (In the formula, R5 is selected from the group consisting of a hydrogen atom and a methyl group, and R6 is an atom. alkyl group, preferably having up to about 15 carbon atoms) It is something. As used herein and in the claims, "alkyl" refers to refers to cyclic and acyclic saturated hydrocarbon groups which may or may not be present. typical soft , non-functional acrylic monomers include butyl acrylate, isobutyl acrylate, Ethylhexyl acrylate, indecyl methacrylate, lauryl methacrylate 2-ethyl methacrylate, including but not limited to tridecyl methacrylate Hexyl acrylate is the preferred soft, non-functional monomer.

Regarding hard monomers, hard monomers include alkylene aromatic monomers and non-functional Including, but not limited to, methacrylic monomers. Description and Claims "Alkylene aromatic monomer" as used in Any containing at least one aliphatic-containing moiety with lekenyl unsaturation “hard monomer” means an organic compound with a homopolymer Tg of about 30″C or more High monomer meaning. Preferred alkenyl aromatic monomers have the following formula (In the formula, X is an aliphatic group having at least one alkenyl bond, and Y is an aromatic ring. substituents, n indicates the number of Y substituents in the ring, n is an integer from O to 5) expressed. Generally, X will be at least 2, but usually no more than about 6, preferably about Contains up to 3 carbon atoms. X is preferably a substituted or unsubstituted alkenyl group be. Preferred substituents on alkenyl groups are halogen atoms, e.g. chlorine. . However, the most preferred alkenyl groups are unsubstituted, i.e. hydrocarbon groups, with 1 Grows only olefinic unsaturated bonds. Ethylene is the most preferred X .

Y is an organic or inorganic group. "group" means any group having at least one carbon atom; "inorganic group" means: means any group that does not have a carbon atom. If n is 2 or more, Y is the same Y generally has 1 to about 15 carbons. atomic group, preferably an aliphatic group. More preferably, Y is a saturated aliphatic group It is. If it is an inorganic group, Y is preferably a halogen atom. Substituents include halo and cyano groups and substituted or unsubstituted groups having from 1 to about 10 carbon atoms. Preferred Y substituents, including substituted alkyl groups, include chlorine atoms, and 1 to about 6 carbon atoms. It is an unsubstituted alkyl group having atoms. Y is more preferably a chlorine atom and A C1 to about C4 unsubstituted alkyl group.

Typical alkenyl aromatic monomers include styrene, p-methylstyrene, and methylstyrene. Styrene, o, p-dimethylstyrene, O+p-diethylstyrene, p-chloros Styrene, isopropylstyrene, t-butylstyrene, 0-methyl-p-isopropylene Includes lopylstyrene, o,p-dichlorostyrene and mixtures thereof. commerce Styrene is the preferred alkenyl aromatic because of its easy availability and low cost. It is an aromatic monomer.

Regarding non-functional methacrylic monomers, typical non-functional methacrylic monomers is the following formula■ to (wherein R1 preferably represents an alkyl group having up to about 6 carbon atoms) Representative non-functional methacrylic monomers represented by are methyl methacrylate, Ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate and mixtures thereof.

In various examples of the invention, the polymer preferably has an average particle size (i.e., maximum cross-section). Generally, in the polymers of the present invention, the average particle size (diameter) is less than about 25 On+w. As the water resistance decreases, the polymer becomes more water resistant. Therefore, the average of the polymer The particle size is preferably about 85 to about 20 on-, more preferably about 90 to about 20 on- About 19 On-1, most preferably about 100 to about 15 On@.

The polymer emulsion optionally contains one or more other components. For example, the polymer emulsion may optionally contain one or more other components. May contain wax. When using a wax, the wax generally increases the water resistance of the thin film produced. Use in sufficient amount to increase sex.

Additionally, the polymer optionally includes a chain transfer agent, which, if used, It is mixed in to adjust the molecular weight of the polymer, and is usually used in the production of polymers. It is used at a concentration of about 0.01 to about 0.5% by weight, based on the amount of monomer present. chain transfer When present, some low molecular weight polymeric components tend to be preferred in PSAs. This is particularly advantageous.

One or more ureido-containing monomers are also optionally present in the polymer. Ido-containing monomers include 2-ureido-ethyl acrylate, 2-ureido-methyl Acrylate, 2-ureido-ethyl acrylamide, 2-ureido-ethylmethane tacrylamide and 1-(2-(3-aloxy-2-hydroxypropylamide) ethyl]imidazolidin-2-one, but are not limited to The new ureido-containing monomer is 1-[2-(3-aloxy-2-hydroxypropyl amino)ethyl]imidasolysin-2-one, which is known as Sibomer (Sip os+er)　Alcolac (AI available from colac). This ureido-containing monomer is generally used for emulsion wetting. Used at a concentration sufficient to enhance adhesive strength, such as from about 0.25% to about 1% by weight of the polymer. There is.

Surfactant-containing species are other optional components present in the polymer. This species is one Generally, the average particle size is less than about 80 nta, preferably from about 25 to about 60 nm. 0 Representative species within the range include alkenyl aromatic monomers, acrylate monomers and and mixtures thereof. Usually styrene and/or butyl acrylate alone. The polymer is used to produce seeds.

The emulsion of the present invention is typically produced by, for example, a delayed addition polymerization method. The delayed addition polymerization process comprises about 25 to about 90% by weight of soft monomer and about 10 to about 75% by weight of soft monomer. % by weight of hard monomers, about 1 to about 5% by weight of olefinic carboxylic acid monomers, and forming a monomer mixture containing from about 0.5 to about 5% by weight crosslinking monomer; water, including water, is added to the reactor and generally at a temperature of about 150 to about 190'F (about 65.6 to about 87 ．． 8°C), during which time the reactor is preferably purged with an inert gas, e.g. nitrogen. A catalyst is then added to the reactor to remove nearly all the oxygen from the reactor. good Preferably, the polymerization focus (e.g. surfactant and/or is a surfactant-containing species) added to the reactor before, simultaneously with, or after the addition of the catalyst. After addition of the catalyst and locus for polymerization forming the charge of the vessel, the monomer mixture Begin delayed addition of The ensuing reaction forms the emulsion of the invention. monomer Addition of the mixture typically takes up to about 3 hours. During the delayed addition of the monomer mixture, Additional catalyst is also typically added to the reactor. In other synthesis steps, monomer mixing A portion of the material, e.g. and/or to the reactor at the same time as the addition of surfactant.

To stabilize the emulsion, the emulsion is typically added near the end of the monomer mixture addition. Adjust the pH of Generally, the pH of the emulsion is at least 6, preferably from about 6 to about 10, most preferably from about 6 to about 8. Adjusting the pH to these ranges As a result, almost all of the olefinic carboxylic acid groups in the polymer are neutralized.

Typically, the pH of the emulsion is adjusted approximately 30 minutes before the end of adding the monomer mixture. Adjust later. Preferably, the pH adjustment is about 1 after the addition of the monomer mixture is complete. Do it within 5 minutes.

After finishing the addition of the monomer mixture, a further catalyst is generally added, during which time the emulsion is A high reaction temperature is maintained to ensure that almost all monomers are polymerized. be When using a catalyst, it is possible to always use the same catalyst. Typical catalysts are 1. t-Butyl hydroperoxide, sodium persulfate, hydrogen peroxide and these including, but not limited to, mixtures.

After all monomer mixture and catalyst have been added, the emulsion is allowed to cool to ambient temperature or is room temperature. Typically, the pH of the cooled emulsion is adjusted to between about 8 and about 10, as required. Arrange. Typically, a base is used on each side to adjust the pH of the emulsion. representative bases consist of amine-containing bases, hydroxide-containing bases and mixtures thereof. selected from the group. Typical bases are dimethylamine, diethylamine, and aminopropylene. Ropatool, ammonium hydroxide and sodium hydroxide, volatile bases Preferred and most preferred is ammonium hydroxide.

This polymerization method produces the polymer emulsion of the invention. The solid content in this emulsion The amount is generally at least about 40% by weight, preferably about 45 to about 60% by weight. It is more preferably within the range of about 45 to about 55% by weight.

When using an emulsion, apply the emulsion to at least a portion of the surface of the substrate. Ru. When dry, the emulsion forms a water-resistant film. Therefore, the emulsion of the present invention is Increases the water resistance of substrates (e.g. particleboard and plywood) when exposed to moisture. strength and/or retain favorable characteristics of the composition (e.g. P SA).

1-1-■ The following examples illustrate the preparation of representative polymer emulsions within the scope of the present invention and emulsion formulations. This particle board was immersed in water. However, the present invention is not limited to these examples. defined by the claims rather than by the claims.

Knee table prepared with a monomer mixture having the composition shown in Table I below. a, ST indicates styrene.

b, 2EHA indicates 2-ethylhexyl acrylate.

c, MAA indicates methacrylic acid.

d, IBMA indicates isobornyl methacrylate.

e, AAEM indicates acetoacetoxyethyl methacrylate.

In each of Examples 1-3, water (approximately 550 g) was added to the reactor and heated; During this time, the reactor was purged with nitrogen. Water at approximately 180″F (approximately 82.2°C) (Example 1-2) or about 160@F (about 71.1°C) (Example 3) When reached, the ingredients listed in Table 1 below were added separately to the reactor.

f, 50s is a dry solid containing styrene species with an average particle size of about 50 nm It represents an emulsion with a content of approximately 30% by weight.

g, 30s is a dry solid containing styrene species with an average particle size of about 30 nm It represents an emulsion with a content of approximately 30% by weight.

Next, the monomer mixture shown in Table I above and about 0.9 g of sodium persulfate are added. and a catalyst solution containing about 27 g of water separately but simultaneously into the reactor. to the reactor over a period of approximately 3 hours, during which time the temperature within the reactor was increased to approximately 185"F. 0″C) (Examples 1-2) or about 165″F (about 73.9°C) (Example 3) It was held either way.

In Examples 1-2, at the end of the 3 hours, the emulsion in the reactor was brought to about room temperature. After cooling, the pH of the emulsion is adjusted to about 8 using about 10% ammonium hydroxide solution. ．． Increased to 5. In Example 3, the addition of catalyst solution and monomer mixture was completed. Immediately after completion of the test, it contains about 5.2 mf of ammonium hydroxide and about 20 mf of water. The solution was added to the emulsion. After cooling the emulsion to room temperature, add 10% ammonium hydroxide. Sufficient amount of um solution was added to raise the pH of the emulsion to about 8.5. emulsion The dry solids content of the liquid and the average particle size of the polymer (Coulter Electronics (Co ulter1!1 electronics) to non-sizer (Non size (measured using a 4-trade name granulometer) is shown in Table 3 below.

1 180 50.3 2 186 49.0 3 133 48.3 11 ■Eng. 8′゛ A monomer mixture and crosslinker solution were prepared. The monomer mixture contains approximately 1470 g styrene, about 1470 g of 2-ethylhexyl acrylate and about 90 g of methane. It consisted of tacrylic acid. The crosslinker solution consists of about 250 g of water and about 12 It contained 5g of N-methylolacrylamide.

Next, water (approximately 2500 g) was added to the reactor and heated, during which time the reaction was The container was replaced. When the water reaches a temperature of approximately 160”F (71.1C), approximately 4.5 g of sodium persulfate and styrene seeds with an average particle size of about 3°n- Approximately 90 g of an emulsion having a dry solids content of 30% by weight was separately added to the reactor.

Next, the monomer mixture and about 4.5 g of sodium persulfate and about 135 g of water were individually added to the reactor contents over a period of approximately 3 hours, during which time the The temperature inside the reactor was maintained at approximately 165”F (73.9°C). Immediately after completing the addition of the polymer mixture, about 50-l of ammonium hydroxide and about A solution containing 100,111 g of water was added to the emulsion. Then reduce the temperature of the emulsion to approx. Raise to 175°F (about 79.4°C) and hold at this temperature for about 1.5 hours; Add additional catalyst solution during the milk to reduce the concentration of any unreacted monomers. The suspension was allowed to cool to room temperature.

After cooling the emulsion to room temperature, a 10% ammonium hydroxide solution was added to the P of the emulsion. Sufficient amount was added to raise the H to about 8.6.

The dry solids content of this emulsion is about 47.2% by weight, and the average particle size of the polymer is about 12%. It was 3 tv.

1 ship 5i2■ Shun on a plate of water One end of the particle board piece was completely coated with the emulsions of Examples 1-4. this Heat the coated particle board pieces at about 180”F (about 82.2C) for about 1 hour. or after drying at room temperature for about a week, first coat the coated edges of each particle board piece. The thickness was measured and then soaked in water for about 16 hours. Coating, dipped edge thickness The thickness was measured and the % increase in thickness (% swelling) was calculated. Control 1. In other words, the uncoated part The same process was repeated using a piece of paperboard. The results are shown in the table below■ Shown below.

5 None (control) 32 6 Example 17 7 Example 25 8 Example 33 9 Example 42 10 Example 42 11 Example 45 12 Example 48 13 Example 46 14 Example 45 15 Example 43 The data shown in Table ■ applies to particleboard coated with an emulsion within the scope of the present invention. Particleboard was found to exhibit a significant reduction in swelling when immersed in water. and

Although the invention has been described in great detail with respect to some preferred embodiments, other embodiments are possible. It is. For example, the emulsion may be modified to improve other thin film and/or emulsion properties. It can contain more than one type of component. Accordingly, this chapter and scope of the appended claims The boxes are not necessarily limited to the description of preferred embodiments described herein.

international search report In+e+ms+1mm1 aH+I6. +mlla PCT/US901 04226 International Search Report PCT/US 90104226

Claims (1)

[Claims] 1. In an emulsion containing (i) a polymer, (ii) water and (iii) a surfactant. wherein the emulsion has less than about 1% by weight surfactant and a total solids content of at least about 40% by weight, and the polymer has (a) a homopolymer Tg of less than about 20°C; 25 to about 90% by weight soft monomer; (b) about 10 to about 75% by weight hard monomer with a homopolymer Tg greater than about 30°C; (c) about 1 to about 5% by weight A polymer emulsion comprising: an olefinic carboxylic acid monomer; and (d) about 0.5 to about 5% by weight of a crosslinking monomer. 2. Claims characterized in that they contain less than about 0.5% by weight surfactant. The emulsion according to Box 1. 3. Particularly, the weight ratio of hard monomer to soft monomer is from about 1:1 to about 1.5:1. The emulsion according to claim 1, wherein the emulsion has the following characteristics. 4. 2. The emulsion of claim 1, wherein the weight ratio of hard monomers to soft monomers is from about 1:4 to about 1:9. 5. Particularly, the weight ratio of hard monomer to soft monomer is from about 1.5:1 to about 3:1. The emulsion according to claim 1, wherein the emulsion has the following characteristics. 6. 2. The emulsion of claim 1, wherein the Tg of said polymer is about -50 to about 50<0>C. 7. Claim 1, wherein the polymer has a Tg of about 0 to about 20°C. emulsion. 8. Claims characterized in that the Tg of the polymer is about -50 to about -35°C. The emulsion according to Box 1. 9. 2. The emulsion of claim 1, wherein said polymer has a Tg of about 30 to about 50<0>C. 10. The emulsion of claim 1, wherein the average particle size of said polymer is less than about 250 nm. 11. The average particle size of the polymer is about 85 to about 200 nm. The emulsion according to claim 1. 12. The average particle size of the polymer is about 90 to about 190 nm. The emulsion according to claim 1. 13. The emulsion of claim 1, wherein the average particle size of said polymer is about 100 to about 150 nm. 14. 2. Emulsion according to claim 1, characterized in that the soft monomer is selected from the group consisting of non-functional acrylic monomers, ethylene and mixtures thereof. 15. The soft monomer has the following formula ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R5 is selected from the group consisting of a hydrogen atom and a methyl group, and R6 is a 2. The emulsion according to claim 1, wherein the emulsion is a non-functional acrylic monomer represented by (representing an alkyl group). 16. 16. Emulsion according to claim 15, characterized in that R6 has up to about 15 carbon atoms. 17. Soft monomers include butyl acrylate, isobutyl acrylate, and ethylhexyl acrylate. selected from the group consisting of syl acrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate and mixtures thereof. The emulsion according to claim 1, wherein the emulsion has the following characteristics. 18. A claim characterized in that the soft monomer is 2-ethylhexyl acrylate. The emulsion according to claim 1. 19. If the hard monomer is an alkenyl aromatic monomer, a non-functional methacrylic monomer or An emulsion according to claim 1, characterized in that it is selected from the group consisting of: and mixtures thereof. 20. The hard monomer has the following formula ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is an aliphatic group having at least one alkenyl bond, and Y is an aromatic ring. is an alkenyl aromatic monomer represented by a substituent (n is an integer of 0 to 5) The emulsion according to claim 1, characterized in that: 21. Alkenyl aromatic monomer is styrene, p-methylstyrene, methylstyrene o,p-dimethylstyrene, o,p-diethylstyrene, p-chlorostyrene , isopropylstyrene, t-butylstyrene, o-methyl-p-isopropylene selected from the group consisting of styrene, o,p-dichlorostyrene and mixtures thereof. The emulsion according to claim 20, characterized in that the emulsion is selected from the group consisting of: 22. 2. The emulsion according to claim 1, wherein the hard monomer is styrene. 23. Claim 1 characterized in that the hard monomer is a non-functional methacrylic monomer represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, R3 represents an alkyl group) Emulsion as described. 24. Claim 23, wherein R7 has up to about 6 carbon atoms emulsion. 25. Emulsion according to claim 1, characterized in that the hard monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate and mixtures thereof. 26. 2. Emulsion according to claim 1, characterized in that the olefinic carboxylic acid monomer is selected from the group consisting of mono- and di-olefinic carboxylic acids and mixtures thereof. 27. 2. Emulsion according to claim 1, characterized in that the olefinic carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof. 28. A claim characterized in that the olefinic carboxylic acid monomer is methacrylic acid. The emulsion according to claim 1. 29. The emulsion contains about 2 to about 4% by weight of olefinic carboxylic acid monomer. The emulsion according to claim 1, characterized in that: 30. The crosslinking monomer is N-methylol acrylamide or N-methylol methacrylate. Ruamide, diacrylate, dimethacrylate, triallyl cyanurate, dia Ryl maleate, methyl acrylamide glycolate methyl ether, following formula ▲ number There are formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is selected from the group consisting of hydrogen atoms and halogen atoms, and R2 is selected from the group consisting of hydrogen atoms, halo, thio, and monovalent organic groups. , R3 is a divalent group, Z is selected from the group consisting of an organic acyl group and a cyano group), and mixtures thereof. The emulsion according to claim 1, characterized in that: 31. A claim characterized in that the crosslinking monomer is N-methylolacrylamide. The emulsion according to claim 1. 32. A claim characterized in that the polymer contains from about 1 to about 3% by weight of crosslinking monomer. The emulsion according to claim 1. 33. The emulsion according to claim 1, further comprising a chain transfer agent. 34. The emulsion of claim 1 further comprising from about 0.01 to about 0.5% by weight of a chain transfer agent. 35. The combined weight percentage of hard and soft monomers present in the polymer is low. An emulsion according to claim 1, characterized in that it is at least about 90% by weight. 36. The combined weight percentage of hard and soft monomers present in the polymer is low. An emulsion according to claim 1, characterized in that it is at least about 95% by weight. 37. the weight ratio of hard monomers to soft monomers is from about 1:1 to about 1.5:1; the polymer contains at least about 90% by weight of hard and soft monomers; (i) and (ii) an average particle size of less than about 250 nm; the soft monomer is selected from the group consisting of non-functional acrylic monomers, ethylene, and mixtures thereof; The hard monomer is an alkenyl aromatic monomer or a non-functional methacrylic monomer. olefinic carboxylic acid monomers are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof; the crosslinking monomer is selected from the group consisting of N-methylolacrylamide; de, N-methylol methacrylamide, diacrylate, dimethacrylate, Realyl cyanurate, diallyl maleate, methylacrylamide glycole Tomethyl ether, the following formula ▲ Numerical formulas, chemical formulas, tables, etc. 3 is a divalent group, Z is selected from the group consisting of an organic acyl group and a cyano group, and mixtures thereof. An emulsion according to claim 1, characterized in that the emulsion is selected from the group consisting of: 38. the emulsion contains less than about 0.5% by weight surfactant; the weight ratio of hard monomer to soft monomer is from about 1:1 to about 1.5:1; contains at least about 95% by weight hard and soft monomers and (i) has a Tg of about 0 to about 20°C; and (ii) about 2 to about 4 weight percent olefin having an average particle size of about 90 to about 200 nm. the soft monomer is 2-ethylhexyl acrylate; the hard monomer is styrene; The acid monomer is methacrylic acid; the crosslinking monomer is N-methacrylic acid. The emulsion according to claim 1, characterized in that it is tyrolacrylamide. 39. the weight ratio of hard monomers to soft monomers is from about 1:4 to about 1:9; the polymer contains at least about 90% by weight of hard and soft monomers; (i) about -50% by weight; and (ii) an average particle size of less than about 250 nm; the soft monomer is from the group consisting of non-functional acrylic monomers, ethylene, and mixtures thereof. the hard monomer is selected from the group consisting of alkenyl aromatic monomers, non-functional methacrylic monomers and mixtures thereof; The rubonic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof; the crosslinking monomer is selected from the group consisting of N-methylol acrylamide, N-methylol methacrylamide, diacrylate, dimethacrylate, Triallyl cyanurate, diallyl maleate, methyl acrylamide glycolate methyl ether, following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R1 is selected from the group consisting of hydrogen atoms and halogen atoms, R2 is hydrogen atom, halo, thio, and a monovalent organic group, R3 is a divalent group, and Z is selected from the group consisting of an organic acyl group and a cyano group). selected from the group consisting of olefinically unsaturated monomers. The emulsion according to claim 1, characterized in that: 40. the emulsion contains less than about 0.5% by weight surfactant; the weight ratio of hard monomer to soft monomer is from about 1:4 to about 1:9; 95% by weight of hard and soft monomers and (i) a Tg of about -50 to about -35°C; and (ii) about 2 to about 4 weight percent olefin having an average particle size of about 90 to about 200 nm. Contains a fin-based carboxylic acid monomer and about 1 to about 3% by weight of a crosslinking monomer; The hard monomer is 2-ethylhexyl acrylate; the hard monomer is styrene. 2. The emulsion according to claim 1, wherein: the olefinic carboxylic acid monomer is methacrylic acid; and the crosslinking monomer is N-methylolacrylamide. 41. the weight ratio of hard monomer to soft monomer is from about 1.5:1 to about 3:1; the body contains at least about 90% by weight of hard and soft monomers and has (i) a Tg of about 30 to about 50°C and (ii) an average particle size of less than about 250 nm; the soft monomers are non-functionalized; A group consisting of acrylic monomers, ethylene, and mixtures thereof. the hard monomer is selected from the group consisting of alkenyl aromatic monomers, non-functional methacrylic monomers and mixtures thereof; The rubonic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof; the crosslinking monomer is selected from the group consisting of N-methylol acrylamide, N-methylol methacrylamide, diacrylate, dimethacrylate, Triallyl cyanurate, diallyl maleate, methyl acrylamide glycolate methyl ether, following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R1 is selected from the group consisting of hydrogen atoms and halogen atoms, R2 is hydrogen atom selected from the group consisting of halo, thio and a monovalent organic group, R3 is a divalent group and Z is selected from the group consisting of an organic acyl group and a cyano group) selected from the group consisting of olefinically unsaturated monomers. The emulsion according to claim 1, characterized in that: 42. the emulsion contains less than about 0.5% by weight surfactant; the weight ratio of hard monomer to soft monomer is from about 1.5:1 to about 3:1; at least about 95% by weight of hard and soft monomers; and (ii) about 2 to about 4 weight percent olefin having an average particle size of about 90 to about 200 nm. Contains a fin-based carboxylic acid monomer and about 1 to about 3% by weight of a crosslinking monomer; The hard monomer is 2-ethylhexyl acrylate; the hard monomer is styrene. 2. The emulsion according to claim 1, wherein: the olefinic carboxylic acid monomer is methacrylic acid; and the crosslinking monomer is N-methylolacrylamide. 43. The emulsion according to claim 1, further comprising seeds. 44. The claim further comprises seeds having an average particle size of less than about 80 nm. The emulsion according to claim 1. 45. It is further characterized by containing a species having an average particle size of about 25 to about 60 nm. The emulsion according to claim 1. 46. Furthermore, alkenyl aromatic monomers, acrylate monomers, and mixtures thereof 2. Emulsion according to claim 1, characterized in that it contains species comprising monomers selected from the group consisting of: 47 (i) in an emulsion containing a polymer, (ii) water and (iii) a surfactant. wherein the emulsion has less than about 1% by weight surfactant and a total solids content of at least about 40% by weight, and the polymer has a Tg of about -50 to about 50°C; (a) A soft monomer whose homopolymer Tg is lower than -20°C; (b) a hard monomer whose homopolymer Tg is higher than about 30°C; (c) about 1 to about 5% by weight of an olefinic carbon. 1. A polymer emulsion comprising: a rubonic acid monomer; and (d) from about 0.5 to about 5% by weight of a crosslinking monomer. 48. An emulsion comprising (i) a polymer and (ii) water, wherein the emulsion has a surface tension greater than about 45 dyn/cm, and the polymer (a) has a homopolymer Tg of about -20 (b) a hard monomer with a homopolymer Tg greater than about 30°C; (c) about 1 to about 5% by weight of an olefinic carbon. 1. A polymer emulsion comprising: a rubonic acid monomer; and (d) from about 0.5 to about 5% by weight of a crosslinking monomer. 49. 49. The emulsion of claim 48, wherein said emulsion has a surface tension of about 45 to about 55 dyn/cm. 50. 50. The emulsion of claim 48, wherein the emulsion has a total solids content of at least about 40% by weight. 51. 50. The emulsion of claim 48, wherein the polymer has a Tg of about -50 to about 50<0>C. 52. It is specified that the emulsion further contains less than about 1% by weight surfactant. 49. The emulsion according to claim 48, wherein the emulsion has the following characteristics. 53. Claims wherein the emulsion contains a total solids content of at least about 40% by weight and further less than about 1% by weight surfactant, and the polymer has a Tg of about -50 to about 50°C. The emulsion according to range 48. 54. A thin film formed by drying the emulsion according to claim 1. 55. 55. A product comprising a substrate having a surface, at least a part of which is coated with a thin film according to claim 54. 56. 2. The emulsion of claim 1, wherein the emulsion contains from about 45% to about 55% total solids by weight. 57. In the method for producing a polymer emulsion, (a) a soft monomer whose homopolymer Tg is lower than about -20°C, a hard monomer whose homopolymer Tg is higher than about 30°C, an olefin (b) about 30 minutes from about 30 minutes before the end of step (a); (b) about 30 minutes before the end of step (a); A method for producing an emulsion, which comprises a subsequent step of adjusting the pH of the emulsion to substantially neutralize all the carboxylic acid groups in the polymer, thereby stabilizing the emulsion. 58. 58. The method of claim 57, further comprising providing a locus for polymerization initiation in the reactor, the locus for polymerization initiation being a surfactant-containing species. 59. 58. The method of claim 57, further comprising providing the reactor with a locus for polymerization initiation, the locus for polymerization initiation being a surfactant. 60. Step (b) includes adding the olefinic carboxylic acid to the reactor for at least 58. A method according to claim 57, characterized in that the method also includes a step of simultaneously adjusting the pH of the emulsion. 61. 58. The method of claim 57, wherein step (b) is initiated within about 30 minutes of adding substantially all of the olefinic carboxylic acid to the reactor. 62. 58. The method of claim 57, wherein step (b) is initiated between about 15 minutes before and about 15 minutes after substantially all of the olefinic carboxylic acid is added to the reactor. 63. 58. The method of claim 57, wherein step (b) comprises adjusting the pH of the emulsion to at least about 6. 64. Particularly, step (b) includes adjusting the pH of the emulsion to between about 6 and about 10. 58. The method according to claim 57. 65. 58. The method of claim 57, wherein step (b) comprises adjusting the pH of the emulsion to between about 6 and about 8. 66. 58. The method of claim 57, wherein step (b) comprises adjusting the pH of the emulsion with a base. 67. 58. The method of claim 57, wherein step (b) comprises adjusting the pH of the emulsion with a volatile base. 68. Step (b) adjusts the pH of the emulsion using an amine-containing base, a hydroxide-containing base and and mixtures thereof. 69. Step (b) comprises adjusting the pH of the emulsion with ammonium hydroxide. 58. The method according to claim 57, characterized in that: 70. (c) adding further catalyst after step (b); and (d) cooling the emulsion after step (c). (e) adjusting the pH of the emulsion to about 8 to about 10 after step (d); 58. The method according to claim 57, characterized in that: 71. 2. The emulsion of claim 1, wherein said polymer further contains a ureide-containing monomer at a concentration sufficient to enhance the wet adhesive strength of the emulsion. 72. An emulsion containing (i) a polymer, (ii) water, and (iii) a surfactant, wherein the emulsion has a surface tension greater than about 45 dyn/cm and less than about 1% by weight. wherein the polymer has a Tg of from about -50 to about 50°C; (a) the homopolymer has a Tg of less than about -20°C; ~90% by weight soft monomer; (b) from about 10% to about 75% by weight hard monomer with a homopolymer Tg greater than about 30°C; (c) from about 1% to about 5% olefin. and (d) about 0.5 to about 5% by weight of a crosslinking monomer. 73. The mixed weight percentage of hard and soft monomers present in the above polymer is low. 73. The emulsion according to claim 72, wherein both are about 90% by weight. 74. The mixed weight percentage of hard and soft monomers present in the above polymer is low. 73. The emulsion of claim 72, wherein both are about 95% by weight. 75. (i) polymer, (ii) water and (iii) surfactant-containing loca for polymerization in an emulsion containing less than about 1% by weight surfactant and at least about 40% total solids; (a) the homopolymer has a Tg lower than about -20°C; (b) about 10 to about 75% by weight of hard monomers with a homopolymer Tg greater than about 30°C; (c) about 1 to about 5% by weight of soft monomers; % of an olefinic carboxylic acid monomer; (d) from about 0.5 to about 5% by weight of a crosslinking monomer; and optionally (e) a wet adhesion promoter. liquid. 76. 76. The emulsion according to claim 75, wherein said polymer mainly consists of a soft monomer, a hard monomer, an olefinic carboxylic acid monomer, and a crosslinking monomer. 77. (i) polymer, (ii) water and (iii) surfactant-containing loca for polymerization in an emulsion containing less than about 1% by weight surfactant and at least about 40% total solids; The above polymer has a Tg of about -50 to about 50°C, and has a main chain and the following formula: (a) ▲ Numerical formula, chemical formula, table, etc. etc. Selected from the group consisting of (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where Y is a substituent on an aromatic ring, n is an integer of 0 to 5, and R is an alkyl group having about 4 to about 8 carbon atoms) attached to the main chain. A polymer emulsion characterized by the following.