Aqueous polymer emulsion and liquid-coated sound-absorbing compound containing the same

Abstract

This invention relates to an aqueous polymer emulsion, a method for producing an aqueous polymer emulsion, a liquid-coated sound-absorbing compound containing an aqueous polymer emulsion, and the use of a polymer emulsion in a liquid-coated sound-absorbing compound.

Description

Technical Field

[0001] The present invention relates to an aqueous polymer emulsion, a method for producing the aqueous polymer emulsion, a liquid-applied sound deadening formulation containing the aqueous polymer emulsion, and the use of the polymer emulsion in the liquid-applied sound deadening formulation.

Background Art

[0002] Noise, vibration, and harshness (NVH) are widespread in vehicles and other fields (e.g., construction materials, household appliances). One of the most common methods for reducing vibration is a bitumen pad, which is a thick patch adhered to metal or plastic parts of the body or frame. This is cumbersome to use. First, it needs to be cut into specific shapes to fit various vehicle modes and various parts. Second, a large storage area is required, and logistics become complicated. Third, it is installed by workers, requires a lot of labor, is overall costly and inefficient. Furthermore, high concentrations of VOCs and odors are harmful to the health of workers and vehicle passengers. Due to the weaknesses of bitumen pads, other technologies such as rubber, PVC, epoxy-based non-aqueous LASD (liquid-applied sound deadening) materials have emerged, but these materials usually contain solvents or plasticizers and are still not very friendly to the environment and health.

[0003] Aqueous (WB) LASD is a newly emerged technology in the past 20 years. The viscoelasticity of polymers brings the possibility of attenuating sound vibrations by heat dissipation when operated near its glass transition temperature (Tg). Compared with the prior art, aqueous LASD has several advantages: 1) It is automated and can be applied by robotic spraying, significantly reducing the required labor. 2) Since there is no need to cut into specific shapes, logistics and storage are simplified. 3) Due to its high attenuation efficiency, the coating film weight can be reduced. 4) A high filler content is possible. 5) Environmentally friendly (solvent-free, low VOC).

[0004] Therefore, there is a great need to provide a lightweight, easily applicable aqueous LASD formulation that exhibits improved damping performance. [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of this disclosure is to provide an aqueous polymer emulsion, which enables the preparation of a lightweight, liquid-coated sound-absorbing compound that exhibits improved adhesion, appearance, and damping performance.

[0006] Another object of this disclosure is to provide a method for preparing polymer emulsions.

[0007] A further object of this disclosure is to provide a liquid-coated sound-absorbing compound comprising a polymer emulsion.

[0008] A further object of this disclosure is to provide the use of the polymer emulsion of the present invention in liquid-coated sound-absorbing formulations. [Means for solving the problem]

[0009] Surprisingly, it was found that the above objective can be achieved by the following embodiments.

[0010] 1. Aqueous polymer emulsions are, (A) A copolymer prepared by polymerization of at least one hydrophobic monoethylene unsaturated monomer (a), a hydrophilic monoethylene unsaturated monomer (b), and at least one functional monomer (c), The functional monomer (c) is selected from the group consisting of: ethylenically unsaturated monomers having an acidic group and / or the corresponding anion; ethylenically unsaturated monomers having an amino group, amide group, ureido group, 1,3-diketo group, hydroxyl group, polyether chain, or N-heterocyclic group and / or protonated with the nitrogen; or alkylated ammonium derivatives thereof. A copolymer in which the functional monomer (c) is different from monomers (a) and (b); and (B) Emulsifier system, wherein the emulsifier system comprises at least one phosphate emulsifier. Includes.

[0011] 2. The aqueous polymer emulsion according to item 1, wherein the total amount of hydrophobic monoethylene unsaturated monomer (a) may be at least 80% by weight, or 80-99% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight, based on the total amount of all monomers.

[0012] 3. The aqueous polymer emulsion according to item 1 or 2, wherein the total amount of hydrophilic monoethylene unsaturated monomer (b) may be at least 0.1% by weight, 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight or less, based on the total amount of all monomers.

[0013] 4. An aqueous polymer emulsion according to any one of items 1 to 3, wherein the hydrophobic monoethylenically unsaturated monomer (a) is selected from the group consisting of (meth)acrylate monomers, (meth)acrylonitrile monomers, styrene monomers, vinyl alkanoate monomers, and monoethylenically unsaturated di and tricarboxylic acid ester monomers.

[0014] 5. The aqueous polymer emulsion according to any one of items 1 to 4, wherein the hydrophilic monoethylene unsaturated monomer (b) is selected from the group consisting of monoethylene unsaturated dicarboxylic acid, acrylic acid, methacrylic acid, and β-carboxyethyl acrylate.

[0015] 6. The aqueous polymer emulsion according to any one of items 1 to 5, wherein the hydrophilic monoethylene unsaturated monomer (b) comprises at least two monomers selected from itaconic acid, acrylic acid, methacrylic acid, and β-carboxyethyl acrylate.

[0016] 7. An aqueous polymer emulsion according to any one of items 1 to 6, wherein the functional monomer (c) comprises at least two monomers selected from the group consisting of ethylenically unsaturated monomers having an acidic group and / or a corresponding anion, an amino group, an amide group, a ureido group, a 1,3-diketo group, a hydroxyl group, a polyether chain, or an N-heterocyclic group, and / or being protonated with the nitrogen, or alkylated ammonium derivatives thereof.

[0017] 8. An aqueous polymer emulsion according to any one of items 1 to 7, wherein the copolymer (A) is prepared by single-phase polymerization.

[0018] 9. An aqueous polymer emulsion according to any one of items 1 to 8, wherein the copolymer (A) is prepared by two-phase polymerization, the monomer of the first phase comprises monomer (a), and (b) and / or (c), the monomer of the second phase comprises monomer (a), and optionally (b) and / or (c), and the weight ratio of the first-phase polymer to the second-phase polymer is in the range of 95:5 to 40:60, preferably in the range of 90:10 to 40:60, more preferably in the range of 90:10 to 50:50.

[0019] 10. An aqueous polymer emulsion according to any one of items 1 to 9, wherein the particle size of the emulsion is in the range of 50 to 300 nm, preferably in the range of 50 to 250 nm, and most preferably in the range of 50 to 200 nm.

[0020] 11. A method for preparing a polymer emulsion as described in item 8 or 10, A method comprising the steps of preparing a copolymer (A) by polymerization of monomer (a), monomer (b), and monomer (c), and adding the emulsifier system (B) before, after, or during polymerization.

[0021] 12. A method for preparing a polymer emulsion as described in item 9 or 10, Step 1: The step of preparing the first phase polymer by polymerizing the monomer of the first phase; Step 2: The step of preparing the second-phase polymer by polymerizing the monomer of the second phase; The steps include adding the emulsifier system (B) before, after, or during polymerization. A method that includes this.

[0022] 13. A liquid-coated sound-absorbing compound containing a polymer emulsion as described in any one of items 1 to 10.

[0023] 14. Use of a polymer emulsion described in any one of items 1 to 10 in a liquid-coated sound-absorbing formulation.

[0024] The aqueous polymer emulsion of the present invention enables the preparation of liquid-coated sound-absorbing formulations exhibiting improved adhesion, appearance, and damping performance (e.g., high loss coefficient, high damping peak, and wide damping curve), which can be applied at a low cost and are lightweight, and the liquid-coated sound-absorbing formulations may have a higher filler content. [Modes for carrying out the invention]

[0025] The following description further illustrates the disclosure with reference to embodiments, so as to be fully understood by those skilled in the art. These embodiments are provided solely for the purpose of better understanding the subject matter of the disclosure and are not intended to impose any limitations on the scope, applicability, or embodiments as described in the claims. Those skilled in the art will understand that, without departing from the spirit of the disclosure, various technical features of each embodiment can be omitted, substituted, or added on a case-by-case basis. Furthermore, technical features described in some embodiments can be combined with those described in other embodiments.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this disclosure pertains.

[0027] In this disclosure, the terms “comprise,” “comprising,” “include,” and “including,” and their various variations, can be understood as open-ended terms meaning “including, but not limited to.” In contrast, “consisting” and its various variations exclude components, steps, or procedures that are not specifically enumerated. The term “embodiment” can be understood as “at least one embodiment.” The term “another embodiment” may be understood as “at least one other embodiment.” Any other terms that may appear but are not explicitly mentioned herein should not be construed or limited in a manner contrary to the underlying concepts of the embodiments of this disclosure unless expressly stated otherwise.

[0028] Throughout this disclosure, the expressions “a,” “an,” “the,” and “one or more” are used interchangeably and are intended to include both singular and plural forms unless the singular form is explicitly specified or clearly indicated by the context. When referring only to the singular form, the term “1” is typically used. The term “or” is generally intended to include the meaning of “and / or” unless the content clearly indicates otherwise. As used herein, “preferred,” “preferred,” and “preferred” refer to embodiments of the disclosure that may provide particular advantages under certain circumstances. However, other embodiments may also be preferred under the same circumstances. Furthermore, the enumeration of one or more preferred embodiments does not mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0029] Unless otherwise specified, all percentages, ppm, parts, and ratios are given by weight. Furthermore, numerical ranges listed by endpoints include all numbers within that range (for example, 5-10 includes 5, 5.1, 5.2, 5.55, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10).

[0030] In the context of this disclosure, any specific value mentioned in a feature (including any specific value mentioned as an endpoint within a range) can be recombined to form a new range.

[0031] Water-based polymer emulsion In one embodiment, the present invention is an aqueous polymer emulsion, (A) A copolymer prepared by polymerization of at least one hydrophobic monoethylene unsaturated monomer (a), a hydrophilic monoethylene unsaturated monomer (b), and at least one functional monomer (c), The functional monomer (c) is selected from the group consisting of: ethylenically unsaturated monomers having an acidic group and / or the corresponding anion; ethylenically unsaturated monomers having an amino group, amide group, ureido group, 1,3-diketo group, hydroxyl group, polyether chain, or N-heterocyclic group and / or protonated with the nitrogen; or alkylated ammonium derivatives thereof. A copolymer in which the functional monomer (c) is different from monomers (a) and (b); and (B) Emulsifier system, wherein the emulsifier system comprises at least one phosphate emulsifier. This relates to aqueous polymer emulsions containing [specific components]. Hydrophobic monoethylene unsaturated monomer (a)

[0032] In one embodiment, the hydrophobic monoethylenically unsaturated monomer (a) is selected from the group consisting of (meth)acrylate monomers, (meth)acrylonitrile monomers, styrene monomers, vinyl alkanoate monomers, and monoethylenically unsaturated di and tricarboxylic acid ester monomers.

[0033] Examples of (meth)acrylate monomers include C1-C 18 Alkyl (meth)acrylates and C3-C 10 Examples include cycloalkyl (meth)acrylates, benzyl (meth)acrylates, phenyl (meth)acrylates, and mixtures thereof.

[0034] C1~C 18 Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)methacrylate, n-lauryl (meth)acrylate, n-tridecyl (meth)acrylate, n-cetyl (meth)acrylate, n-stearyl (meth)acrylate, isomiristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate (ISTA). C1~C 12 Alkyl (meth)acrylates, particularly C1-C6 alkyl (meth)acrylates, are preferred.

[0035] C3~C 10 Specific examples of cycloalkyl (meth)acrylates include isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, or cyclohexyl methacrylate.

[0036] In one embodiment, the hydrophobic monoethylene unsaturated monomer (a) is composed of two or more C1-C12 18 Alkyl (meth)acrylates and C3-C 10 Cycloalkyl (meth)acrylate, preferably two C1-C 18It may contain an alkyl (meth)acrylate.

[0037] In particular, the styrene monomer may be unsubstituted styrene or C1-C6-alkyl-substituted styrene, for example, styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, ortho-, meta- and para-ethylstyrene, o,p-dimethylstyrene, o,p-diethylstyrene, isopropylstyrene, o-methyl-p-isopropylstyrene or any mixture thereof, but is not limited thereto.

[0038] In particular, the vinyl alkanoate monomer is C2-C 11 Vinyl esters of alkanoic acids (for example, C2-C6-alkanoic acids), for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl versatate, or mixtures thereof, may be used, but are not limited thereto.

[0039] In particular, the monoethylenically unsaturated di- and tricarboxylic acid ester monomers may be complete esters of monoethylenically unsaturated di- and tricarboxylic acids, for example, diethyl maleate, dimethyl fumarate, ethyl methyl itaconate, or any mixture thereof, but are not limited thereto.

[0040] In a preferred embodiment, the hydrophobic monoethylenically unsaturated monomer (a) comprises two hydrophobic monoethylenically unsaturated monomers.

[0041] In a preferred embodiment according to the present invention, one or more C1-C 12 Alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or mixtures thereof, are selected as at least one hydrophobic monoethylenically unsaturated monomer (a).

[0042] According to the present invention, the hydrophobic monoethylene unsaturated monomer (a) is different from the functional monomer (c).

[0043] The total amount of hydrophobic monoethylene unsaturated monomer (a) may be at least 80% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight, based on the total amount of all monomers. In one embodiment, the total amount of hydrophobic monoethylene unsaturated monomer (a) may be in the range of 80-99% by weight, or 85-98% by weight, or 90-97% by weight, based on the total amount of all monomers.

[0044] Hydrophilic monoethylene unsaturated monomer (b) In one embodiment, the hydrophilic monoethylene unsaturated monomer (b) comprises a carboxyl group or its anhydride.

[0045] In one embodiment, the hydrophilic monoethylene unsaturated monomer (b) comprises at least two (e.g., two, three, or four) hydrophilic monoethylene unsaturated monomers.

[0046] In particular, hydrophilic monoethylene unsaturated monomers include, but are not limited to, monoethylene unsaturated carboxylic acids such as (meth)acrylic acid, β-carboxyethyl acrylate, itaconic acid, fumaric acid, citraconic acid, sorbic acid, cinnamic acid, glutaconic acid, and maleic acid; and monoethylene unsaturated carboxylic acid anhydrides such as itaconic anhydride, fumaric anhydride, citraconic anhydride, sorbic acid anhydride, cinnamic acid anhydride, glutaconic acid anhydride, and maleic acid anhydride.

[0047] In a preferred embodiment, the hydrophilic monoethylenically unsaturated monomer (b) includes itaconic acid, methacrylic acid, or a mixture thereof. In a more preferred embodiment, the hydrophilic monoethylenically unsaturated monomer (b) includes a mixture containing itaconic acid or methacrylic acid, for example, a mixture containing itaconic acid and methacrylic acid, a mixture containing itaconic acid and acrylic acid, a mixture containing methacrylic acid and acrylic acid, or a mixture containing itaconic acid, methacrylic acid, and acrylic acid.

[0048] The total amount of hydrophilic monoethylene unsaturated monomer (b) may be at least 0.1% by weight and 20% by weight or less (for example, 0.2% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, 2% by weight, 5% by weight, 10% by weight, or 15% by weight), preferably 15% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight or less, based on the total amount of all monomers. In one embodiment, the total amount of hydrophilic monoethylene unsaturated monomer (b) may be in the range of 0.1 to 20% by weight, 0.2 to 15% by weight, 0.5 to 10% by weight, or 1 to 5% by weight, based on the total amount of all monomers. Functional monomer (c)

[0049] According to the present invention, functional monomer (c) is selected from the group consisting of ethylenically unsaturated monomers having an acidic group and / or its corresponding anion, an amino group, an amide group, a ureido group, a 1,3-diketo group, a hydroxyl group, a polyether chain, or an N-heterocyclic group and / or being protonated with nitrogen, or alkylated ammonium derivatives thereof, wherein functional monomer (c) is different from monomer (a) and monomer (b).

[0050] In the present invention, the acidic group described for functional monomer (c) does not include a carboxyl group. In one embodiment, the acidic group can be selected from a sulfonic acid group, a phosphonic acid group, or a phosphoric acid group.

[0051] In one embodiment, the functional monomer (c) comprises at least two functional monomers.

[0052] Examples of ethylenically unsaturated monomers having an acidic group and / or its corresponding anion include monoethylenically unsaturated sulfonic acids, such as vinyl sulfonic acid, styrene sulfonic acid, acrylic oxyethane sulfonic acid, and acrylamide-2-methylpropanesulfonic acid, and their salts, especially alkali metal salts; monoethylenically unsaturated phosphonic acids, such as vinyl phosphonic acid, allyl phosphonic acid, styrene phosphonic acid, and 2-acrylamido-2-methylpropanephosphonic acid, and their salts, especially alkali metal salts; and furthermore, monoethylenically unsaturated phosphoric acid, and its salts, especially alkali metal salts.

[0053] Examples of ethylenically unsaturated monomers having an amide group include monoethylenically unsaturated amides, such as (meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethylacrylamide (DMA), 2-hydroxyethyl(meth)acrylamide, and dimethylaminoethylmethacrylamide.

[0054] Examples of ethylenically unsaturated monomers having a hydroxyl group include hydroxyalkyl (e.g., C2-C6 alkyl) esters of monoethylenically unsaturated carboxylic acids (e.g., (meth)acrylic acid), such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, and glycerol (meth)acrylate.

[0055] Examples of ethylenically unsaturated monomers containing a 1,3-diketo group are monomers containing a 1,3-diketo group (e.g., acetoacetoxyethyl (meth)acrylate or diacetone acrylamide).

[0056] Examples of ethylenically unsaturated monomers containing a ureido group include monomers containing a urea group (e.g., ureidoethyl (meth)acrylate, acrylamide glycolic acid, and methacrylamide glycolic acid methyl ether).

[0057] Examples of ethylenically unsaturated monomers having a polyether chain include monomers containing a polyalkylene oxide chain, preferably monomers containing an alkylene oxide having 2 to 6 carbon atoms, more preferably 2 to 4, or 2 or 3, most preferably 2 carbon atoms, where the alkylene oxide may be ethylene oxide, propylene oxide, or a mixture thereof. The molecular weight of the polyether chain may be in the range of 132 to 3000, or 250 to 2000, or 300 to 1500, or 300 to 1000. In one embodiment, the ethylenically unsaturated monomer having a polyether chain has one (meth)acrylate (ester) group.

[0058] The N-heterocyclic ring described for monomer (c) may have 1 to 3 nitrogen atoms. In addition to nitrogen atoms, the ring may optionally have 1 to 2 more heteroatoms (e.g., N, O, or S). The N-heterocyclic ring may have 5 or 6 ring members. Examples of ethylenically unsaturated monomers having an N-heterocyclic group are 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 4-vinylimidazole, 1-vinylpyrazole, or 1-vinyl-1,2,4-triazole.

[0059] In preferred embodiments, the functional monomer (c) includes an ethylenically unsaturated monomer having an acidic group and / or its corresponding anion, an ethylenically unsaturated monomer having a 1,3-diketo group, an ethylenically unsaturated monomer having a hydroxyl group or an ethylenically unsaturated monomer having a polyether chain, or a mixture of two, three or four of these monomers. In preferred embodiments, the functional monomer (c) includes an ethylenically unsaturated monomer having an acidic group and / or its corresponding anion, an ethylenically unsaturated monomer having a 1,3-diketo group, and an ethylenically unsaturated monomer having a hydroxyl group.

[0060] The functional monomer (c) is present in an amount of 0.5 to 15% by weight (e.g., 1.0, 1.5, 2, 2.5, 3, 4, 5, 8, 10, or 12% by weight), preferably 1.0 to 10% by weight, and more preferably 1.5 to 5% by weight, based on the total amount of all monomers.

[0061] In this context, the expression “a copolymer prepared by polymerization of” or similar expressions used for component (A) does not mean a closed-end form. In addition to monomers (a), (b), and (c), further monomers may be included as needed.

[0062] Emulsifier-based (B) According to the present invention, the emulsifier system comprises at least one phosphate emulsifier.

[0063] Phosphate emulsifiers are compounds of formulas (I), (II), or mixtures thereof: [R 11 O(AO) m ][R 12 O(AO) n ]P(=O)(OM 11 ) (I) R 11 O(AO) m P(=O)(OM 11 )(OM 12 ) (II) (In the formula, R 11 and R 12 It is independently C6~C 30 Alkyl, benzene, and benzene derivatives, where m and n are independently integers from 0 to 20, and AO is alkylene oxy. 11 and M 12 (These are independently H or cationic ions.) You can choose from these options.

[0064] R 11 and R 12 Independently, C6~C 30 These are alkyl, benzene, and benzene derivatives. C6~C 30 Alkyls are linear / branched / cyclic C6~C 30Alkyl, preferably linear / branched / cyclic C8-C 25 Alkyl, more preferably linear / branched / cyclic C8~C 20 Alkyl compounds can be selected. Benzene and benzene derivatives include benzene, C1-C 15 Alkylbenzyl, C1-C 20 Alkylbenzoates and aryloxys can be selected. Preferably, benzene and benzene derivatives are benzene, C2-C 12 Alkylbenzyl, C2~C 15 Alkylbenzoates and aryloxys can be selected. More preferably, benzene and benzene derivatives are benzene, C4-C8 alkylbenzyl, C4-C 10 Alkylbenzoates and aryloxys can be selected.

[0065] The numbers m and n are independently integers between 0 and 20 (e.g., 1, 2, 3, 4, 5, 6, 8, 10, 12, 15, 16, or 18), preferably between 1 and 15, more preferably between 1 and 12, and most preferably between 2 and 12.

[0066] AO is an alkylene oxy, which can preferably have 2 to 6 or 2, 3 or 4 carbon atoms, and can preferably be selected from (-CH2CH2O-), (-CH2CH2CH2O-), and (-CH2(CH3)CHO-).

[0067] M 11 and M 12 These are independently H or cationic ions, such as Li + kaNa + , K + and NH4 +Many of the above compounds are commercially available, such as Rhodafac RS410, RS610, RS710 and PE3501 (manufactured by Solvay), Disponil FEP 3825 PN, Disponil FEP 6300 and Maphos 24T (manufactured by BASF), and TERIC 305 (manufactured by Huntsman).

[0068] The compounds of formula (I) or formula (II) may be used individually or in combination.

[0069] The amount of the phosphate emulsifier, preferably the compound or combination of formula (I) or formula (II), may be 0.2 to 10% by weight, preferably 0.5 to 8% by weight, more preferably 1 to 5% by weight, and most preferably 1 to 4% by weight, based on the total weight of the aqueous polymer emulsion. Emulsifier system (B) can be added before, after, or during polymerization.

[0070] In addition to the compound of formula (I) or formula (II), other suitable emulsifiers may be used. These emulsifiers include, but are not limited to, at least one nonionic, anionic, or cationic emulsifier.

[0071] Nonionic emulsifiers in emulsifier systems are selected from the group consisting of ethoxylated mono-, di-, and tri-alkylphenols and ethoxylated fatty alcohols, or alkylphenols / fatty alcohols having polymerizable moieties. For example, Lutensol® A(C), a trademark available from BASF SE. 12 C 14 Fatty alcohol ethoxylate, EO degree: 3-8), trademark Lutensol (registered trademark) AO(C 13 C 15 Oxo alcohol ethoxylate, EO degree: 3-30), trademark Lutensol (registered trademark) AT(C 16 C 18 Fatty alcohol ethoxylate, EO degree: 11-80), trademark Lutensol (registered trademark) ON(C10 Oxo alcohol, EO degree: 3-11), trademark Lutensol (registered trademark) TO(C 13 Examples include oxo alcohols (EO degree: 3-20).

[0072] The anionic emulsifiers in the emulsifier system are selected from the group consisting of alkali metal salts and ammonium salts of alkyl sulfates, sulfate monoesters of ethoxylated alkanols and ethoxylated alkylphenols, alkyl sulfonic acids, alkylaryl sulfonic acids, and combinations thereof.

[0073] Suitable anionic emulsifiers include compounds of general formula (III). [ka] (In the formula, R 1 and R 2 is an H atom or C1~C 24 It is an alkyl radical, however, R 1 and R 2 It is not H, but M 1 and M 2 This also includes alkali metal ions and / or ammonium ions. In general formula (III), R 1 and R 2 It preferably has 6 to 18 carbon atoms, more preferably 6 carbon atoms. 1 and M 2 The most preferred is sodium, potassium, or ammonium sodium. Particularly advantageous is M 1 and M 2 All of them are sodium, and R 1 R is a branched alkyl group with 12 carbon atoms. 2 is an H atom or R 1 That is the case.

[0074] Furthermore, the cationic emulsifier in the emulsifier system is selected from the group consisting of positively charged amines and quaternary ammonium compounds.

[0075] The amount of emulsifier system (B) may be 0.2 to 12% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, and most preferably 1.2 to 5% by weight, based on the total weight of the aqueous polymer emulsion.

[0076] The amount of copolymer (A) may range from 8 to 70% by weight, preferably 15 to 60% by weight, more preferably 25 to 60% by weight, and most preferably 35 to 60% by weight, based on the total weight of the aqueous polymer emulsion.

[0077] The emulsion according to the present invention may have a solid content in the range of 10 to 70% by weight, preferably 20 to 60% by weight, more preferably 30 to 60% by weight, and most preferably 40 to 60% by weight.

[0078] In one embodiment, copolymer (A) is prepared by single-phase polymerization.

[0079] In another embodiment, copolymer (A) is prepared by two-phase polymerization, where the first-phase monomer comprises monomers (a), (b), and / or (c), and the second-phase monomer comprises monomer (a), and optionally (b), and / or (c), and the weight ratio of the first-phase polymer to the second-phase polymer is in the range of 95:5 to 40:60, preferably in the range of 90:10 to 40:60, and more preferably in the range of 90:10 to 50:50. In this regard, if the first-phase monomer does not contain monomer (b), the second-phase monomer contains monomer (b). If the first-phase monomer does not contain monomer (c), the second-phase monomer contains monomer (c).

[0080] The glass transition temperature (Tg) of copolymers obtained by emulsion polymerization is, in principle, in the range of -30 to 30°C (e.g., -25, -20, -15, -10, -5, 0, 5, 10, 20, or 25°C), preferably -20 to 20°C, or -10 to 10°C. In this specification, the glass transition temperature (Tg) is understood to mean the actual glass transition temperature, which is the midpoint temperature determined by differential scanning calorimetry (DSC) according to ASTM D3418-82 [see also Ullmann's Encyclopedia of Industrial Chemistry, p. 169, Verlag Chemistry, Weinheim, 1992].

[0081] The theoretical glass transition temperature can be calculated from the monomers used in emulsion polymerization. The theoretical glass transition temperature is usually calculated from the monomer composition using Fox's formula: 1 / Tg t =x a / Tg a +x b / Tg b +....x n / Tg n ,

[0082] In this equation, x a , x b ,....x n is the mass fraction of monomers a, b, ..., n, and Tg a , Tg b ,....Tg nTg is the actual glass transition temperature in Kelvin units of a homopolymer synthesized from only one of monomers 1, 2, ..., n at a time. Fox's formula is described by TGFox in Bull. Am. Phys. Soc. 1956, 1, page 123, and similarly in Ullmann's Encyclopadie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol. 19, p. 18, 4th ed., Verlag Chemie, Weinheim, 1980. The actual Tg values ​​for homopolymers of most monomers are publicly known and are listed, for example, in Ullmann's Encyclopadie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 5th ed., vol. A21, p. 169, Verlag Chemie, Weinheim, 1992. Further sources of information on the glass transition temperatures of homopolymers include, for example, J. Brandrup, E. H. Mergut, Polymer Handbook, 1st Ed., J. Wiley, New York 1966, 2nd Ed., J. Wiley, New York 1975, 3rd Ed., J. Wiley, New York 1989, and 4th Ed., J. Wiley, New York 2004.

[0083] Typically, the theoretical glass temperature Tg is calculated according to Fox as described herein. t The experimentally determined glass transition temperatures described herein are similar or identical, and do not deviate from each other by more than 5K, and especially not by more than 2K. Therefore, both the actual and theoretical glass transition temperatures of the copolymers are determined by the appropriate monomers Ma, Mb...Mn and their mass fractions x in the monomers so that they reach the desired glass transition temperatures Tg(1) and Tg(2), respectively. a , x b ,....x nThis can be adjusted by selecting appropriate amounts of monomers Ma, Mb...Mn to obtain a copolymer and / or copolymer phase having a desired glass transition temperature, which is common knowledge to those skilled in the art.

[0084] In one embodiment, the theoretical glass transition temperature of the polymer obtained as a result of being formed in one phase is approximately the same as, or at least 10°C, particularly at least 20°C or at least 40°C different from, the theoretical glass transition temperature of the polymer obtained as a result of being formed in another phase. The calculation of the theoretical glass transition temperature will be explained below.

[0085] In one embodiment, the theoretical glass transition temperature of the second-phase polymer is approximately the same as, or at least 10°C higher than, the theoretical glass transition temperature of the first-phase polymer, and particularly at least 20°C or at least 40°C higher.

[0086] Naturally, the theoretical glass transition temperature of a polymer formed from one phase can only differ from that of a polymer formed from the other phase by no more than 10°C or 5°C.

[0087] In one embodiment, the theoretical glass transition temperature of the first-phase polymer is in the range of -30 to 30°C (e.g., -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, or 25°C), preferably in the range of -20 to 20°C, -10 to 10°C, or -5 to 5°C.

[0088] In preferred embodiments, the aqueous polymer emulsion of the present invention has a particle size in the range of 50 to 300 nm, preferably in the range of 50 to 250 nm, and most preferably in the range of 50 to 200 nm.

[0089] According to the present invention, copolymer (A) is neutralized.

[0090] Method for preparing polymer emulsions One aspect of the present invention is a method for preparing a polymer emulsion according to the present invention, A copolymer (A) is prepared by polymerization of monomer (a), monomer (b), and monomer (c), and an emulsifier system (B) is added before, after, or during polymerization. Regarding methods including

[0091] The emulsion preparation method of this disclosure may be single-phase polymerization or multi-phase emulsion polymerization. In single-phase polymerization, the overall composition of monomers supplied to the polymerization reaction under polymerization conditions remains the same or nearly the same, whereas in multi-phase emulsion polymerization, the overall composition of monomers supplied to the polymerization reaction under polymerization conditions remains nearly the same or, in particular, is changed at least once such that the stoichiometric glass transition temperature of the polymer resulting from the formation of one phase differs from the stoichiometric glass transition temperature of the polymer resulting from the formation of another phase by at least 10°C, particularly at least 20°C or at least 40°C.

[0092] In one embodiment, the theoretical glass transition temperature of a polymer resulting from formation in one phase is approximately the same as, or at least 10°C, particularly at least 20°C or at least 40°C different from, the theoretical glass transition temperature of a polymer resulting from formation in another phase. Naturally, the difference between the theoretical glass transition temperature of a polymer resulting from formation in one phase and the theoretical glass transition temperature of a polymer resulting from formation in the other phase can be no more than 10°C or 5°C.

[0093] In one embodiment, the method of the present invention is carried out as a two-phase emulsion polymerization (i.e., the composition of monomers supplied to the polymerization reaction under polymerization conditions is changed once) or as a three-phase or four-phase emulsion polymerization (i.e., the composition of monomers supplied to the polymerization reaction under polymerization conditions is changed two or three times).

[0094] One aspect of the present invention relates to a method for preparing a polymer emulsion of the present invention, wherein the copolymer (A) is prepared by two-phase polymerization, and this method is Step 1: Prepare a first-phase polymer by polymerizing the first-phase monomer; Step 2: Next, prepare the second-phase polymer by polymerizing the second-phase monomer; Steps to add emulsifier system (B) before, after, or during polymerization. Includes.

[0095] Polymerization occurs in the presence of an initiator that forms radicals under reaction conditions. The initiator may be a peroxide or an azo compound. Of course, redox initiator systems are also considered.

[0096] The peroxides used may, in principle, be inorganic peroxides and / or organic peroxides. Suitable examples of inorganic peroxides include hydrogen peroxide and persulfates, such as mono- or di-alkali metal or mono- or di-ammonium salts of persulfate, examples of which are mono- and di-sodium, -potassium, or -ammonium salts, such as sodium persulfate, potassium persulfate, and ammonium persulfate. Suitable examples of organic peroxides include alkyl hydroperoxides such as tert-butyl hydroperoxide, aryl hydroperoxides such as p-menthyl hydroperoxide or cumene hydroperoxide, dialkyl or diaryl peroxides such as di-(tert-butyl)peroxide, and benzoyl peroxide or di-cumene peroxide, and peroxyesters.

[0097] The azo compounds used are essentially 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(N,N'-dimethylisobutyroamidine) dihydrochloride, and 2,2'-azobis(amidinopropyl) dihydrochloride.

[0098] A redox initiator system is a composite system consisting of at least one organic or inorganic reducing agent and at least one oxidizing agent. The oxidizing agent intended for a redox initiator system is essentially the peroxide described above. As corresponding reducing agents, low-oxidation sulfur compounds, such as alkali metal sulfites (e.g., potassium sulfite and / or sodium sulfite), alkali metal bisulfites (e.g., potassium bisulfite and / or sodium bisulfite), alkali metal metabisulfites (e.g., potassium metabisulfite and / or sodium metabisulfite), acetone bisulfite, formaldehyde sulfoxylates (e.g., potassium formaldehyde sulfoxylate and / or sodium formaldehyde sulfoxylate), alkali metal salts, specifically potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogen sulfide, such as potassium hydrogen sulfide and / or sodium hydrogen sulfide, for example, salts of polyvalent metals, such as iron(II) sulfate, iron(II) ammonium sulfate, iron(II) phosphate, etc., enediols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing sugars, such as sorbose, glucose, fructose and / or dihydroxyacetone, can be used.

[0099] Preferred initiators include peroxide-type initiators, such as hydrogen peroxide, tert-butyl hydroperoxide, di-(tert-butyl)peroxide, benzoyl peroxide, and peroxyesters; persulfates, such as sodium persulfate, potassium persulfate, and ammonium persulfate; and azo-based initiators.

[0100] Polymerization is generally carried out by using 0.1 to 5% by weight of a radical initiator, preferably 0.5 to 4% by weight, based on the total amount of monomers.

[0101] The initiation of a polymerization reaction refers to the start of the polymerization reaction of monomers present in the polymerization vessel due to the decomposition of a radical initiator. Polymerization begins, for example, when the polymerization mixture contains monomers and inorganic peroxides and reaches a temperature in the range of 60°C to 125°C, preferably 70°C to 100°C, more preferably 80°C to 95°C.

[0102] In addition to the above components, molecular weight modifiers may be used during emulsion polymerization to reduce / correct the molecular weight of the copolymer obtained by polymerization. These mainly consist of aliphatic and / or aromatic halogen compounds, e.g., halogenated hydrocarbons, e.g., n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene chloride, chloroform, bromoform, bromotrichloromethane, dibromomethylene chloride, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, and organosulfur compounds, e.g., aliphatic primary, secondary or tertiary mercaptans, e.g., ethyl mercaptan, n-butyl Ropyl mercaptan, 2-propyl mercaptan, n-butyl mercaptan, 2-methyl-2-propyl mercaptan, n-pentyl mercaptan, 2-pentyl mercaptan, 3-pentyl mercaptan, 2-methyl-2-butyl mercaptan, 3-methyl-2-butyl mercaptan, n-hexyl mercaptan, 2-hexyl mercaptan, 3-hexyl mercaptan, 2-methyl-2-pentyl mercaptan, 3-methyl-2- Pentyl mercaptan, 4-methyl-2-pentyl mercaptan, 2-methyl-3-pentyl mercaptan, 3-methyl-3-pentyl mercaptan, 2-ethylbutyl mercaptan, 2-ethyl-2-butyl mercaptan, n-heptyl mercaptan and its isomers, n-octyl mercaptan and its isomers, n-nonyl mercaptan and its isomers, n-decyl mercaptan and its isomers, n-undecyl mercaptan and its isomers, n-dodecyl mercaptan and its isomers, n-tridecyl mercaptan and its isomers, substituted mercaptans, e.g., 2-hydroxyethyl mercaptan, tertiary dodecyl mercaptan, aromatic mercaptans, e.g., benzenethiol, o-benzenethiol, m- or p-methylbenzenethiol, and Polymer Handbook, 3rd edition, 1989, J. Brandrup and E.H.All other substances described in Immergut, John Wiley & Sons, section II, sulfur compounds on pages 133–141, as well as aliphatic and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde, and / or benzaldehyde; unsaturated fatty acids, such as oleic acid; dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane; olefins, such as cyclohexene, α-methylstyrene and its dimers; or hydrocarbons with readily removable hydrogen atoms, such as toluene.

[0103] The total amount of molecular weight modifier used in emulsion polymerization is generally 5% by weight or less, often 3% by weight or less, and often 1% by weight or less, based on the total monomers. In one embodiment, the total amount of molecular weight modifier used in emulsion polymerization is in the range of 0.1 to 5% by weight, or 0.2 to 3% by weight, based on the total monomers.

[0104] In one embodiment, polymer seeds are used. Polymer seeds are particularly used when it is desired to set the particle size of polymer particles obtained by aqueous emulsion polymerization to a specific value (see, for example, U.S. Patent No. 2,520,959 and U.S. Patent No. 3,397,165). Seeds may be used in amounts of 0.01 to 5% by weight, usually 0.05 to 3% by weight, and often 0.1 to 2.5% by weight, based on the total amount of monomer in each case.

[0105] One type of polymer seed used is polymer seed particles with a particle size of 60 nm or less, typically 5 nm to 50 nm, and typically 15 nm to 35 nm, as measured by light scattering.

[0106] When using polymer seeds, it is advantageous to use exogenous polymer seeds. Unlike in-situ polymer seeds, which have the same monomer composition as polymers prepared in the reaction vessel before the actual emulsion polymerization reaction begins and are subsequently initiated by an aqueous emulsion polymerization reaction initiated by free radicals, exogenous polymer seeds are polymer seeds prepared in a separate reaction step and have a different monomer composition than polymers prepared by the aqueous emulsion polymerization reaction. However, this simply means that different monomers, or monomer compositions with different compositions, are used for preparing exogenous polymer seeds and for preparing copolymers. The preparation of exogenous polymer seeds is well known to those skilled in the art and is generally achieved by introducing relatively small amounts of monomer and relatively large amounts of surfactant as initial inputs into a reaction vessel and adding a sufficient amount of polymerization initiator at the reaction temperature.

[0107] According to the present invention, it is preferable to use exogenous polymer seeds having a glass transition temperature exceeding 50°C, typically 60-100°C, and often 70-100°C. Polymer seeds of polystyrene or polymethyl methacrylate are particularly preferred.

[0108] Initially, the entire amount of exogenous polymer seeds may be added to the polymerization vessel. Alternatively, only a portion of the exogenous polymer seeds may be included in the initial additions to the polymerization vessel, with the monomers added during polymerization along with the remaining portion. However, if necessary, the entire amount of polymer seeds may be added during polymerization. Preferably, the entire amount of exogenous polymer seeds is initially added to the polymerization vessel before initiating the polymerization reaction.

[0109] The polymerization reaction may be carried out at a temperature of 60°C to 125°C, preferably 70°C to 100°C, more preferably 80°C to 95°C, for 1 to 10 hours, preferably 2 to 8 hours, and more preferably 4 to 6 hours.

[0110] After polymerization, residual monomers are generally removed for deodorization by chemical and / or physical processes, etc. Typical chemical and / or physical deodorization processes are known to those skilled in the art [see, for example, EP-A771328, DE-A19624299, DE-A19621027, DE-A19741184, DE-A19741187, DE-A19805122, DE-A19828183, DE-A19839199, DE-A19840586 and 19847115]. Chemical deodorization processes can be carried out by adding further radical initiators from the group of initiators described above to the reaction mixture, or by extending such additions to carry out so-called "post-polymerization," in other words, polymerization to achieve a conversion rate of 95-99%. In most cases, after the addition of monomers is complete, it is sufficient to stir the reaction mixture at the polymerization temperature for 0.1 to 3 hours, preferably 0.5 to 2 hours, and more preferably 0.5 to 1 hour. A physical deodorization process may be carried out by stripping with steam or an inert gas to reduce the monomer content.

[0111] The solids content is adjusted to the desired value by dilution or concentration, or the resulting aqueous emulsion is mixed with further conventional additives, such as fungicides, foaming modifiers, or viscosity modifiers.

[0112] The solid content was measured by drying a specified amount of emulsion (approximately 2 g) in an aluminum crucible with an inner diameter of approximately 5 cm in a drying cabinet at 130°C for 2 hours until it reached a certain weight. Two separate measurements were performed. The values ​​reported in the examples are the average of the two measurements.

[0113] Emulsions obtained by emulsion polymerization generally have a solid content of 10-70% by weight, usually 20-65% by weight, and frequently 25-60% by weight, based entirely on the emulsion. The particle size is generally in the range of 50-300 nm, preferably 50-250 nm, and most preferably 50-200 nm. The particle size can be determined by dynamic light scattering (DLS) using Malvern HPPS.

[0114] Liquid-coated sound-absorbing compound One aspect of the present invention relates to a liquid-coat type sound-absorbing compound comprising the polymer emulsion of the present invention.

[0115] The amount of polymer emulsion of the present invention may range from 10 to 60% by weight (e.g., 15, 20, 25, 30, 40, 50, or 60% by weight) or from 15 to 50% by weight or from 20 to 40% by weight, based on the total weight of the liquid-coated sound-absorbing formulation.

[0116] In some embodiments, the damping formulation may include at least one of the following: fillers, defoamers, rheological modifiers, emulsifiers (i.e., “dispersing agents” or “dispersants”), flocculants, pigments, or biocides.

[0117] In some embodiments, the damping formulation may contain one or more fillers that constitute 40% to 90% by weight, or 45% to 85% by weight, or 50% to 80% by weight, or any value or partial range within these ranges of the formulation. Examples of fillers include, but are not limited to, calcium carbonate, barium sulfate, glass fillers, magnesium carbonate, plastic microspheres, mica, powdered slate, montmorillonite flakes, glass flakes, metal flakes, graphite, graphene, talc, iron oxide, clay minerals, cellulose fibers, mineral fibers, carbon fibers, glass or polymer fibers or beads, ferrite, calcium carbonate, calcium magnesium carbonate, calcium silicate, barite, crushed natural or synthetic rubber, silica, aluminum hydroxide, alumina, and mixtures thereof. In some embodiments, the damping formulation may contain any two or more such fillers, for example, a mixture of calcium carbonate and mica.

[0118] In some embodiments, the damping formulation may contain a defoaming agent (defoamer). Examples of defoaming agents include Foamaster® S (BASF), Rhodoline® DF 540 (Solvay), Rhodoline® 635 (Solvay), Foamaster® MO 2170 (BASF), Foamaster® MO 2190 (BASF), or Dehydran SE 2 (BASF). The damping formulation may contain an amount of defoaming agent necessary to provide the desired foaming properties. In some embodiments, the defoaming agent may constitute less than 1% by weight of the damping formulation. In some embodiments, the damping formulation may contain up to 1% by weight of defoaming agent, with a weight greater than 0%.

[0119] In some embodiments, the damping formulation may contain a thickener or rheological modifier. Examples of thickeners and rheological modifiers include Rheovis® HS 1152, Rheovis® HD 1152 (BASF), or Rheovis® AS 1130 (BASF), or Attagel 40 (BASF). The damping formulation may contain an amount of rheological modifier necessary to provide the desired solution properties. In some embodiments, the formulation may contain less than 1% by weight of rheological modifier. In other embodiments, the formulation may contain more than 0% by weight up to 1% by weight (e.g., 0.2, 0.5, 0.8% by weight) of thickener or rheological modifier.

[0120] In some embodiments, the damping formulation includes a dispersant. A non-limiting example of a dispersant is Dispex® CX 4320 (manufactured by BASF). The damping formulation may contain an amount of dispersant necessary to provide the formulation with the desired properties. In some embodiments, the formulation may contain 0.1 to 2.0% by weight, or 0.25 to 1.5% by weight, or 0.5 to 1.0% by weight, or any value or sub-range within these ranges.

[0121] Pigments or combinations of pigments can also be used in the formulations of the present invention. While they may have other properties, pigments can also be used to increase the solid content of the formulation and to function as fillers. Generally, alkali-stable inorganic or organic pigments can be used in the formulations of the present invention. Examples of pigments useful in the present invention include carbon black. Commercially available pigments include Aurasperse from BASF Corporation; Xfast schwarz 0066 from BASF; and Tint Ayd from Chromaflo Technologies. Preferably, they are present in an amount of 0.2–5.0% by weight or 0.2–2.0% by weight, based on the total weight of the formulation.

[0122] In some embodiments, the decayed formulation may include a biocide. Non-limiting examples of suitable biocides include Acticide® MBS (a mixture of 1,2-benzoisothiazolin-3-one (2.5%) and 2-methyl-4-isothiazolin-3-one (2.5%)), Acticide® MV-14 (a mixture of 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one in a 3:1 ratio), and Acticide® CEM 2 (a mixture of 1,2-benzoisothiazol-3(2H)-one (9.3-10.7%), 2-methylisothiazol-3(2H)-one (4.7-5.2%), and 5-chloro-2-methyl-2H-isothiazol-3-one (0.9-1.1%)).

[0123] In some embodiments, the damping compound may be deposited on the surface of the mechanical vibration source in the form of a layer. The thickness of such a layer may be in the range of 0.5 mm to 12 mm, or 0.5 mm to 10 mm, or 1.0 mm to 10 mm, or 1.5 mm to 8 mm, or 2 mm to 6 mm, or any value or partial range within these ranges.

[0124] The damping formulations provided herein can also be applied to a variety of materials, including, for example, metals, steel, aluminum, plastics, wood, wall panels, or gypsum board.

[0125] The decayed formulation may have a viscosity in the range of 30,000 cPs to 120,000 cPs or 40,000 cPs to 100,000 cPs at 25°C, or any value or sub-range within these ranges.

[0126] The formulation can be prepared by mixing the components until a uniformly dispersed mixture is obtained. Any conventional mixing technique can be used. The resulting formulation has storage stability. The formulation of the present invention can be applied to the surface of a suitable substrate using conventional coating techniques such as spray coating or brushing.

[0127] This disclosure, described in general terms as above, will be more readily understood by referring to the following examples, which are provided as illustrations and are not intended to limit the invention.

[0128] A further aspect of the present invention relates to the use of the polymer emulsion of the present invention in liquid-coated sound-absorbing formulations.

[0129] Examples

[0130] [Table 1A] [Table 1B]

[0131] 2. Test Method Sintering characteristics are defined as the heat resistance of the LASD formulation. To prepare the samples, the LASD formulation was used to fill 2 mm and 4 mm molds on a steel panel, then the molds were removed and the mixture was heated at 140°C for 30 minutes. After cooling to room temperature, the state of the sintered formulation was observed.

[0132] For damping performance (composite loss factor (CLF), loss factor) testing, samples were prepared by coating a steel rod (245 mm × 10 mm × 1 mm) with the compound. This was then dried at 80°C for 15 minutes and then at 140°C for 25 minutes. After cooling to room temperature, the dried compound was cut into 180 mm length × 10 mm width pieces and placed in an Oberst testing machine in an environmental chamber for composite loss factor testing. The test protocol followed ASTM E 756. The loss factor was tested at 10, 20, 30, 40, and 50°C, with the peak value considered the highest CLF value and the peak damping temperature being its corresponding temperature. A higher loss factor indicates better damping performance of the compound.

[0133] Adhesion is defined as the ability of a compound to coat a steel rod. Low adhesion means that the interaction between the steel and the compound is weak, and therefore the test sample cannot withstand sample preparation or decay testing.

[0134] Example 1 - Preparation of aqueous polymer emulsion Preparation of emulsion a1 (single-phase polymerization) 266.4 g of deionized water, 2.4 g of IA, and 8.0 g of seed were added to a 2 L four-necked glass flask, and the reactor was heated to 88°C with stirring. Next, 22.8 g of sodium persulfate (7% solution) was added to the reactor and held for 5 minutes. After this, the reactor was heated to 90°C, and a feed mixture prepared with 389.6 g of BA, 372.0 g of MMA, 12.0 g of HEMA, 8.0 g of AAEMA, 32.0 g of Gopanol VS (25% solution), 4.0 g of AA, 4.0 g of MAA, 5.6 g of tDMK, 12.0 g of RS610, 2.4 g of FES77, and 376.0 g of deionized water was fed to the reactants over 4 hours. During this time, 36.8 g of sodium persulfate (7% solution) was fed to the reactor along with the mixture over 4 hours. After supply, the reaction was allowed to proceed for 30 minutes. Once the dispersion had cooled, 9.20 g of 20% ammonia solution was added for neutralization. The final dispersion was filtered before further characterization and formulation. The resulting dispersion had a pH of 5.3 and a solids content of 50.8% by weight.

[0135] Preparation of emulsions a2, b1-b6, c1-c6, and v1-v3 (single-phase polymerization) The procedure for preparing emulsion a1 was repeated, except that emulsions a2, b1-b6, c1-c6, and v1-v3 were prepared using the feed mixtures shown in Tables 1, 2, and 3, respectively. In addition to the components shown in Tables 1, 2, and 3, the feed mixture further contained 5.6 g of tDMK and 376.0 g of deionized water.

[0136] Emulsions v1 and v2 did not contain phosphate emulsifiers and were comparative emulsions.

[0137] Emulsion v3 did not contain functional monomer (c) and was a comparative emulsion.

[0138] The corresponding formulations prepared using these comparative emulsions were also comparative formulations.

[0139] Example 2 - Preparation of a liquid-coated sound-absorbing compound Preparation of formulation A1 Formulation A1 was prepared by sequentially mixing 90.0 g of emulsion a1, 6.6 g of water, 1.5 g of Dehydran SE 2, 2.4 g of Dispex CX4230, 0.9 g of Xfast schwarz 0066, 150.0 g of 325 mesh CaCO3, 45.0 g of 325 mesh black mica, and 3.6 g of Attagel 40 with mechanical stirring. The viscosity of the final formulation was 70,000 ± 20,000 cPs, and the solids content was 80 ± 5% by weight.

[0140] Preparation of formulations A2, B1-B6, C1-C6, and V1-V3 The preparation procedure for formulation A1 was repeated, except that emulsion a1 was replaced with emulsion a2, emulsions b1-b6, emulsions c1-c6, and emulsions v1-v3, respectively, to prepare formulations A2, B1-B6, C1-C6, and V1-V3.

[0141] The damping performance, firing characteristics, and adhesion characteristics of the liquid-coated sound-absorbing compound are also shown in Tables 1, 2, and 3.

[0142] [Table 2]

[0143] [Table 3]

[0144] [Table 4]

[0145] The results in Tables 1, 2, and 3 show that the liquid-coated sound-absorbing (LASD) formulations prepared from the emulsion according to the present invention exhibit improved adhesion, appearance, and attenuation performance, such as a high loss coefficient, a high attenuation peak, and a wide attenuation curve (attenuation range CLF > 0.1). Comparative LASD formulations prepared from the emulsion without the use of phosphate emulsifiers showed poor appearance (V1 and V2). Comparative LASD formulation prepared from the emulsion without the use of functional monomers (V3) failed the test because the slurry easily peeled off the substrate.

[0146] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. Accordingly, the present invention is intended to encompass modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. It is an aqueous polymer emulsion, (A) A copolymer prepared by polymerization of at least one hydrophobic monoethylene unsaturated monomer (a), a hydrophilic monoethylene unsaturated monomer (b), and at least one functional monomer (c), The functional monomer (c) is selected from the group consisting of: ethylenically unsaturated monomers having an acidic group and / or its corresponding anion; ethylenically unsaturated monomers having an amino group, amide group, ureido group, 1,3-diketo group, hydroxyl group, polyether chain, or N-heterocyclic group and / or being protonated with nitrogen; or alkylated ammonium derivatives thereof. A copolymer in which the functional monomer (c) is different from monomer (a) and monomer (b); and (B) Emulsifier system, wherein the emulsifier system comprises at least one phosphate emulsifier. A water-based polymer emulsion containing [a specific component].

2. The aqueous polymer emulsion according to claim 1, wherein the total amount of hydrophobic monoethylene unsaturated monomer (a) may be at least 80% by weight, or 80 to 99% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight, based on the total amount of all monomers.

3. The aqueous polymer emulsion according to claim 1 or 2, wherein the total amount of hydrophilic monoethylene unsaturated monomer (b) may be at least 0.1% by weight, 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight or less, based on the total amount of all monomers.

4. The aqueous polymer emulsion according to any one of claims 1 to 3, wherein the hydrophobic monoethylenically unsaturated monomer (a) is selected from the group consisting of (meth)acrylate monomers, (meth)acrylonitrile monomers, styrene monomers, vinyl alkanoate monomers, and monoethylenically unsaturated di and tricarboxylic acid ester monomers.

5. The aqueous polymer emulsion according to any one of claims 1 to 4, wherein the hydrophilic monoethylene unsaturated monomer (b) is selected from the group consisting of monoethylene unsaturated dicarboxylic acid, acrylic acid, methacrylic acid, and β-carboxyethyl acrylate.

6. The aqueous polymer emulsion according to any one of claims 1 to 5, wherein the hydrophilic monoethylene unsaturated monomer (b) comprises at least two monomers selected from itaconic acid, acrylic acid, methacrylic acid, and β-carboxyethyl acrylate.

7. The aqueous polymer emulsion according to any one of claims 1 to 6, wherein the functional monomer (c) comprises at least two monomers selected from the group consisting of: an ethylenically unsaturated monomer having an acidic group and / or its corresponding anion; an ethylenically unsaturated monomer having an amino group, an amide group, a ureido group, a 1,3-diketo group, a hydroxyl group, a polyether chain, or an N-heterocyclic group and / or being protonated with the nitrogen; or alkylated ammonium derivatives thereof.

8. The aqueous polymer emulsion according to any one of claims 1 to 7, wherein the copolymer (A) is prepared by single-phase polymerization.

9. The aqueous polymer emulsion according to any one of claims 1 to 8, wherein the copolymer (A) is prepared by two-phase polymerization, the monomer of the first phase comprises monomer (a), and (b) and / or (c), the monomer of the second phase comprises monomer (a), and optionally (b) and / or (c), and the weight ratio of the first-phase polymer to the second-phase polymer is in the range of 95:5 to 40:60, preferably in the range of 90:10 to 40:60, and more preferably in the range of 90:10 to 50:

50.

10. The aqueous polymer emulsion according to any one of claims 1 to 9, wherein the particle size of the emulsion is in the range of 50 to 300 nm, preferably in the range of 50 to 250 nm, and most preferably in the range of 50 to 200 nm.

11. A method for producing the polymer emulsion according to claim 8 or 10, A method comprising the steps of preparing a copolymer (A) by polymerization of monomer (a), monomer (b), and monomer (c), and adding the emulsifier system (B) before, after, or during polymerization.

12. A method for producing the polymer emulsion according to claim 9 or 10, Step 1: The step of preparing the first phase polymer by polymerizing the monomer of the first phase; Step 2: The step of preparing the second phase polymer by polymerizing the monomer of the second phase; The steps include adding the emulsifier system (B) before, after, or during polymerization. A method that includes this.

13. A liquid-coated sound-absorbing compound comprising the polymer emulsion described in any one of claims 1 to 10.

14. Use of the polymer emulsion according to any one of claims 1 to 10 in a liquid-coated sound-absorbing compound.

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