Emulsifier for emulsion polymerization

Abstract

To provide a method for improving the acid resistance of a coated film formed from a resin emulsion.SOLUTION: An emulsifier for emulsion polymerization comprising a compound represented by formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an emulsifier for emulsion polymerization. [Background technology]

[0002] As regulations on VOCs (volatile organic compounds) become stricter, attention is being paid to aqueous, low-pollutant synthetic resin emulsions made using emulsion polymerization as an alternative to solvent-based resins used in applications such as paints, adhesives, paper coatings, impregnation agents, and textile processing agents.

[0003] Examples of emulsifiers for emulsion polymerization used in emulsion polymerization methods include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers, and anionic surfactants such as polyoxyethylene alkyl sulfates and polyoxyethylene alkyl phenyl sulfates. These emulsifiers for emulsion polymerization not only form micelles to solubilize monomers and stably disperse polymer particles, but also affect the physical properties of the resulting resin emulsion.

[0004] As emulsifiers for emulsion polymerization, ether-type nonionic surfactants obtained by adding an alkylene oxide such as ethylene oxide to nonylphenol, and anionic surfactants obtained by sulfate esterification of these surfactants, are widely used because they have characteristics such as little generation of aggregates and good polymerization stability. For example, Patent Document 1 discloses that a compound having a propenyl structure in nonylphenol is excellent in the stability of resin emulsions and in the water resistance of the resulting polymer films. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 62-221431 Summary of the Invention [Problem to be solved by the invention]

[0006] According to the investigations of the present inventors, it has been found that when a coating film is formed using a resin emulsion prepared by emulsion polymerization using the emulsifier described in Patent Document 1, there is a problem in that the coating film has low acid resistance. For example, a coating film applied to an outdoor facility may be affected by acid rain and may deteriorate. From the viewpoint of expanding the applications of resin emulsions more widely, it is necessary to improve the acid resistance of resin emulsions.

[0007] Therefore, an object of the present invention is to provide a means for improving the acid resistance of a coating film made of a resin emulsion. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by preparing a resin emulsion by emulsion polymerization using an emulsifier for emulsion polymerization having a specific structure, thereby completing the present invention.

[0009] That is, according to one embodiment of the present invention, a compound represented by the following formula (1):

[0010] [ka]

[0011] In formula (1), R 1 represents a saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms, A represents a linear or branched alkylene group having 2 to 4 carbon atoms. n represents the average number of moles of oxyalkylene groups added represented by AO, and is a number from 1 to 80; m is Q + represents the valence of 1 or 2, Q + represents an alkali metal cation, an alkaline earth metal cation, or a nitrogen-containing compound cation, An emulsifier for emulsion polymerization is provided, which comprises a compound represented by the formula: [Effects of the Invention]

[0012] The emulsifier for emulsion polymerization according to the present invention can improve the acid resistance of a coating film made of a resin emulsion. DETAILED DESCRIPTION OF THE INVENTION

[0013] The following describes in detail the embodiments of the present invention. The embodiments described herein are merely illustrative examples for embodying the technical concept of the present invention and are not intended to limit the present invention. Therefore, all other possible embodiments, methods of use, and operational techniques conceivable by those skilled in the art without departing from the spirit of the present invention are within the scope and spirit of the present invention, as well as within the scope of the claims and their equivalents. The embodiments described herein can be arbitrarily combined to produce other embodiments. Furthermore, in this specification, the term "X to Y" indicating a range means "X or more and Y or less," and "weight," "weight %," "mass %," and "parts by weight" and "parts by mass" are treated as synonyms. Unless otherwise specified, measurements of operations and physical properties are performed at room temperature (20-25°C) and a relative humidity of 40-60% RH.

[0014] As used herein, the term "(meth)acrylic" encompasses both acrylic and methacrylic. Thus, for example, the term "(meth)acrylic acid" encompasses both acrylic acid and methacrylic acid. Similarly, the term "(meth)acrylate" encompasses both acrylate and methacrylate, and the term "(meth)acrylamide" encompasses both acrylamide and methacrylamide.

[0015] <Emulsifier for emulsion polymerization> One aspect of the present invention is a compound represented by the following formula (1):

[0016] [ka]

[0017] The present invention relates to an emulsifier for emulsion polymerization, which comprises a compound represented by the formula:

[0018] In formula (1), R 1 represents a saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms. The saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms may be linear or branched. Examples of the saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms include alkyl groups such as tridecyl, tetradecyl, pentadecyl, hexadecyl, and heptadecyl; tridec-8-enyl, tridec-4,7-dienyl, tridec-2,10,12-trienyl, tridec-2,6,10-trienyl, tetradec-7-enyl, tetradec-9-enyl, tetradec-3,8-dienyl, tetradec-9,12-dienyl, pentadec-7-enyl, pentadec-8-enyl, and pentadeca-10-enyl. and alkenyl groups such as a pentadeca-10,14-dienyl group, a pentadeca-7,10-dienyl group, a pentadeca-7,10,14-trienyl group, a hexadeca-4-enyl group, a hexadeca-7-enyl group, a hexadeca-9-enyl group, a hexadeca-7,10-dienyl group, a hexadeca-7,10,13-trienyl group, a heptadec-8-enyl group, a heptadec-11-enyl group, a heptadeca-8,11-dienyl group, a heptadeca-11,14-dienyl group, and a heptadeca-8,11,14-trienyl group; 1 is preferably a saturated or unsaturated straight-chain hydrocarbon group having 13 to 17 carbon atoms, more preferably a straight-chain alkyl group having 13 to 17 carbon atoms or a straight-chain alkenyl group having 13 to 17 carbon atoms.

[0019] According to one embodiment, the compound represented by formula (1) of the present invention is a compound derived from cardanol. Therefore, the compound represented by formula (1) is preferably derived from cardanol, and R 1 is preferably a group derived from cardanol. In addition, when the compound represented by formula (1) is derived from cardanol (R1 is a group derived from cardanol) means that the compound represented by formula (1) is n -SO3 - This means that the R 1 is preferably a pentadecyl group, a pentadec-7-enyl group (pentadeca-7(Z)-enyl group), a pentadec-10-enyl group (pentadeca-10(Z)-enyl group), a pentadeca-7,10-dienyl group (pentadeca-7(Z),10(Z)-dienyl group), or a pentadeca-7,10,14-trienyl group (pentadeca-7(Z),10(Z),14(Z)-trienyl group).

[0020] R 1 Since the compound represented by formula (1) has an unsaturated bond, it is thought that the compound represented by formula (1) acts as a crosslinking agent in the resin emulsion, increasing the degree of polymerization of the resin emulsion, and thereby increasing the film resistance strength of the coating film formed from the resin emulsion.

[0021] In formula (1), A represents a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of linear or branched alkylene groups having 2 to 4 carbon atoms include ethylene (-CHCH-), methylmethylene (-CH(CH)-), trimethylene (-CHCHCH-), 2-methylethylene (-CH-CH(CH)-), tetramethylene (-CHCHCHCH-), 1-methyltrimethylene (-CH(CH)CHCH-), 2-methyltrimethylene (-CHCH(CH)CH-), 1,1-dimethyldimethylene (-C(CH)(CH)CH-), and 1,2-dimethyldimethylene (-CH(CH)CH(CH)-). These alkylene groups, together with an oxygen atom, form an oxyalkylene group. The oxyalkylene groups (AO groups) may be the same or a mixture of different groups (block or random), and are preferably oxyethylene groups (A is an ethylene group) alone, oxypropylene groups (A is a 2-methylethylene group) alone, or a mixture of oxyethylene groups and oxypropylene groups (block or random), more preferably oxyethylene groups or oxypropylene groups, and particularly preferably oxyethylene groups (A is an ethylene group).

[0022] In formula (1), n represents the average number of moles of oxyalkylene groups added represented by AO, and is a number from 1 to 80. n is preferably from 2 to 70, more preferably from 3 to 60, even more preferably from 5 to 50, particularly preferably from 5 to 40, and most preferably from 5 to 30. According to one embodiment, n is from 5 to 60.

[0023] In equation (1), m is Q + represents the valence of the atom, which is either 1 or 2. + If is a monovalent cation, m is 1 and Q + If is a divalent cation, m is 2.

[0024] In equation (1), Q +represents an alkali metal cation, an alkaline earth metal cation, or a nitrogen-containing compound cation. Examples of alkali metal cations include sodium cation, potassium cation, and lithium cation. Examples of alkaline earth metal cations include calcium cation and magnesium cation. Examples of nitrogen-containing compound cations include ammonium ion (NH4 + ) or organic amine cations. Examples of organic amine cations include cations derived from organic amines, such as alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as monoethylamine, diethylamine, and triethylamine; and polyamines such as ethylenediamine and triethylenediamine. In one embodiment, Q + is preferably an alkali metal cation or a nitrogen-containing compound cation, and more preferably a sodium cation, a potassium cation, an ammonium ion (NH4 + ) is more preferred, sodium cation, ammonium ion (NH4 + ) is more preferred. That is, in a preferred embodiment, Q + is a sodium ion, a potassium ion, or an ammonium ion.

[0025] For example, when a resin emulsion is used as a paint for exterior walls, etc., it is thought that it will deteriorate due to various influences such as ultraviolet rays, temperature, humidity, acid rain, and contact with flying debris. In particular, resin emulsions have not yet achieved a satisfactory level of durability against acid. It has been discovered that the emulsifier for emulsion polymerization according to the present invention has good polymerization stability and, when used as an emulsifier for emulsion polymerization, the resulting resin emulsion exhibits excellent acid resistance. Furthermore, the emulsifier for emulsion polymerization according to the present invention has low foaming properties, and when used as an emulsifier for emulsion polymerization, the resulting resin emulsion also exhibits low foaming properties and is easy to handle.

[0026] The reason why the emulsifier for emulsion polymerization according to the present invention exhibits the above-mentioned effects is unclear, but is thought to be as follows: The compound represented by formula (1) has a polyoxyalkylene group and a long-chain hydrocarbon chain in a meta-position relationship on the benzene ring. In a resin emulsion, the hydrophilic polyoxyalkylene group of the compound represented by formula (1) interacts with the surface of emulsion particles in the resin emulsion. Therefore, it is thought that the compound represented by formula (1) is adsorbed to or associated with emulsion particles in the resin emulsion. As a result, it is thought that the compound represented by formula (1) is adsorbed to the emulsion particle surface in a oriented state with a certain degree of regularity due to intermolecular interactions between the benzene rings. In this case, it is presumed that the long-chain hydrocarbon chain located at the meta-position of the polyoxyalkylene group on the benzene ring of the compound represented by formula (1) is oriented along the emulsion particle surface. This is thought to result in the emulsion particles being covered with the long-chain hydrocarbon chain. That is, since the emulsion particles in the resin emulsion are covered with the compound represented by formula (1) (long-chain hydrocarbon chain), it is thought that the long-chain hydrocarbon chain protects the emulsion particles from erosion by acids and the like even when a coating film is formed. For this reason, it is thought that the emulsifier for emulsion polymerization according to the present invention exhibits excellent acid resistance. However, the present invention is not limited to the above mechanism.

[0027] Examples of the compound represented by formula (1) include compounds represented by the following formulas (1-a) to (1-d). In the following formulas (1-a) to (1-d), A, Q + and n are the same as in equation (1).

[0028] [ka]

[0029] The compound represented by formula (1) is preferably a compound represented by formulas (1-e) to (1-h). In the following formulas (1-e) to (1-h), Q +and n are the same as in equation (1).

[0030] [ka]

[0031] Examples of the compound represented by the above formula (1) include the following compounds.

[0032] 1) 3-[7(Z),10(Z),14(Z)-pentatrienyl]phenylpolyoxyethylene(9) sulfate ammonium salt 2) 3-[7(Z),10(Z)-pentadienyl]phenylpolyoxyethylene(9) sulfate ammonium salt 3) 3-[7(Z)-pentadecenyl]phenylpolyoxyethylene(9) sulfate ammonium salt 4) 3-[10(Z)-Pentadecenyl]phenylpolyoxyethylene(9) sulfate ammonium salt 5) 3-Pentadecylphenylpolyoxyethylene(9) sulfate ester ammonium salt 6) 3-[7(Z),10(Z),14(Z)-pentatrienyl]phenylpolyoxyethylene(9) sulfate sodium salt 7) 3-[7(Z),10(Z)-pentadienyl]phenylpolyoxyethylene(9) sulfate sodium salt 8) 3-[7(Z)-Pentadecenyl]phenylpolyoxyethylene(9) sulfate sodium salt 9) 3-[10(Z)-Pentadecenyl]phenylpolyoxyethylene(9) sulfate sodium salt 10) 3-pentadecylphenylpolyoxyethylene(9) sulfate sodium salt.

[0033] In the above examples, polyoxyethylene (9) indicates that an average of 9 moles of oxyethylene groups are added.

[0034] The compounds represented by formula (1) may be used in combination of two or more kinds.

[0035] The compound represented by formula (1) is a saturated or unsaturated hydrocarbon group (R 1 A desired number of moles of alkylene oxide are added to the hydroxyl groups of a phenolic compound substituted with a cation (Q) in the presence of a base catalyst such as sodium hydroxide or potassium hydroxide, according to a conventional method. The phenolic compound is then sulfated using a sulfating agent such as sulfuric anhydride, chlorosulfonic acid, sulfamic acid, or sulfuric acid, and the sulfated product is neutralized with a base to give a cation (Q). + ) to give a compound of formula (1).

[0036] A saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms (R 1 The phenolic compounds substituted with a saturated or unsaturated hydrocarbon group (R) having 13 to 17 carbon atoms may be either an industrially produced pure product or a mixture of several types; or a pure product or a mixture of several types extracted and purified from natural products such as plants. 1Examples of phenolic compounds substituted with a substituted phenol (corresponding to the formula (I)) include 3-[7(Z),10(Z),14-pentadecatrienyl]phenol, 3-[7(Z),10(Z)-pentadecadienyl]phenol, 3-[7(Z)-pentadecenyl]phenol, 3-[10(Z)-pentadecenyl]phenol, and 3-pentadecylphenol, which are extracted from cashew nut shells and the like and are collectively known as cardanol; and 3-[8(Z),11(Z),14(Z)-heptadecatrienyl]phenol, 3-[8(Z),11(Z)-heptadecadienyl]phenol, 3-[12(Z)-heptadecenyl]phenol, and 3-[10(Z)-heptadecenyl]phenol, which are extracted from ginkgo seeds and leaves, Chinese alder leaves, and the like. Among these, cardanol is preferably used because the coating film formed from the resin emulsion obtained by emulsion polymerization has good acid resistance. In the present invention, 3-pentadecylphenol, in which the unsaturated hydrocarbon group has been hydrogenated, is also considered to be cardanol and is referred to as hydrogenated cardanol. Cardanol containing a non-hydrogenated unsaturated hydrocarbon group is referred to as unsaturated cardanol. A compound in which an alkylene oxide is added to hydrogenated cardanol or unsaturated cardanol is referred to as a "hydrogenated cardanol alkylene oxide adduct," and after the hydrogenated cardanol alkylene oxide adduct is sulfated, a cation (Q + ) is referred to as "sulfuric acid ester salt of hydrogenated cardanol alkylene oxide adduct."

[0037] A preferred use of the compound represented by formula (1) is as an emulsifier for emulsion polymerization. By carrying out emulsion polymerization using the compound according to the present invention as an emulsifier for emulsion polymerization, excellent polymerization stability is achieved, and the acid resistance of the coating film formed from the resulting resin emulsion is remarkably excellent. In addition, the resulting resin emulsion has low foaming properties.

[0038] There are no particular limitations on the monomer (polymerizable monomer) that can be emulsion polymerized using the emulsifier for emulsion polymerization according to the present invention, and conventionally known polymerizable monomers (hereinafter also simply referred to as "monomers") can be used. Examples of such monomers include esters of acrylic acid or methacrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; vinyl halides such as vinyl bromide, vinyl chloride, and vinylidene chloride; vinyl esters of fatty acids such as acetic acid, propionic acid, and tertiary synthetic saturated carboxylic acids; aromatic vinyls such as styrene and α-methylstyrene; monoolefins or conjugated diolefins such as ethylene and butadiene; vinyl cyanides such as acrylonitrile; α,β-unsaturated amides such as acrylamide; and α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

[0039] The polymerization initiator may be any initiator typically used for emulsion polymerization, without any particular limitation. Examples of the polymerization initiator include inorganic peroxides such as potassium, sodium, or ammonium persulfates (e.g., ammonium peroxodisulfate) or perborates, and hydrogen peroxide; organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, and peracetic acid; and radical-generating polymerization initiators such as 2,2-azobisisobutyronitrile, 4-azobis-(4-cyanopentanoic) acid, or an alkali metal salt thereof. The amount used is preferably 0.01 to 3.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, and even more preferably 0.1 to 1.0 part by mass, relative to 100 parts by mass of the polymerizable monomer.

[0040] Furthermore, when a peroxide is used as a polymerization initiator, if necessary, the peroxide can be used in combination with a reducing agent such as ascorbic acid, a soluble sulfite, a hydrosulfite, or a thiosulfate. Alternatively, the peroxide can be used as a redox polymerization initiator in combination with a metal monomer that generates heavy metal ions in water or a metal compound that generates metal ions in water, such as ferrous sulfate.

[0041] A chain transfer agent may also be used in combination, such as t-dodecyl mercaptan, dodecyl mercaptan, carbon tetrachloride, chloroform, or triphenylmethane.

[0042] Furthermore, additives commonly used in emulsion polymerization techniques can be used, such as chelating agents, buffers, salts of organic acids, solvents, etc. As the solvent, in addition to water, organic solvents such as alcohols, glycols, glycol ethers, etc. can be used, but water is preferably used as the solvent.

[0043] The amount of the emulsifier for emulsion polymerization containing the compound represented by formula (1) according to the present invention is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 1 to 5 parts by mass of the compound represented by formula (1) relative to 100 parts by mass of the polymerizable monomer.

[0044] In emulsion polymerization using the emulsifier for emulsion polymerization according to the present invention, the compound represented by formula (1) alone sufficiently exhibits its function, but if necessary, it can also be used in combination with a conventionally known surfactant, reactive emulsifier, high-molecular-weight emulsifier, protective colloid, etc. Examples of surfactants that can be used in combination include anionic surfactants such as long-chain alkyl sulfates, long-chain alkylbenzene sulfonates, polyoxyethylene alkyl phenyl ether sulfates, and alkyl diphenyl ether disulfonates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, and Pluronic surfactants.

[0045] Examples of polymeric emulsifiers that can be used in combination include polyvinyl alcohol, poly(meth)acrylates, and polyhydroxyalkylene (meth)acrylates. Examples of protective colloids that can be used in combination include anionic protective colloids such as sodium alginate, and nonionic protective colloids such as hydroxyethyl cellulose.

[0046] When used in combination with an anionic surfactant, a nonionic surfactant, a polymer emulsifier and / or a protective colloid, the amount of each is suitably about 0.05 to 10 parts by mass per part by mass of the compound according to the present invention.

[0047] In the present invention, the resin emulsion can be obtained by a commonly known emulsion polymerization method, such as (1) a batch method, (2) a monomer addition method, or (3) a monomer emulsion addition method, with the monomer emulsion addition method being preferred.

[0048] The present invention also provides a polymer composition obtainable by the above-described emulsion polymerization. That is, according to another aspect of the present invention, there is also provided a resin emulsion containing an emulsion polymer of a composition containing the emulsifier for emulsion polymerization according to the present invention, a polymerizable monomer, and a solvent (particularly preferably water).

[0049] The resin emulsion obtained in this manner can be incorporated into, for example, paints, adhesives, film coating agents, impregnation agents, or fiber processing agents. The resin emulsion of the present invention has improved acid resistance, and as described above, the coating film formed by the resin emulsion has excellent acid resistance. Therefore, adhesives, film coating agents, impregnation agents, or fiber processing agents incorporating the resin emulsion of the present invention can exhibit excellent acid resistance. For example, when applied to a substrate installed outdoors, the high acid resistance can effectively prevent deterioration. Furthermore, the resin emulsion of the present invention also has the property of low foaming. Therefore, adhesives, film coating agents, impregnation agents, or fiber processing agents incorporating the resin emulsion of the present invention also have the advantage of excellent handleability.

[0050] Although the embodiments of the present invention have been described in detail, it is clear that this is by way of illustration and example only and not of limitation, and that the scope of the present invention should be interpreted by the appended claims.

[0051] The present invention encompasses the following aspects and configurations.

[0052] [1] Formula (1):

[0053] [ka]

[0054] In formula (1), R 1 represents a saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms, A represents a linear or branched alkylene group having 2 to 4 carbon atoms. n represents the average number of moles of oxyalkylene groups added represented by AO, and is a number from 1 to 80; m is Q + represents the valence of 1 or 2, Q + represents an alkali metal cation, an alkaline earth metal cation, or a nitrogen-containing compound cation, an emulsifier for emulsion polymerization, comprising a compound represented by the formula: [2] The emulsifier for emulsion polymerization according to the above [1], wherein the compound is a compound derived from cardanol; [3]R 1 the emulsifier for emulsion polymerization according to the above [1] or [2], wherein is a saturated or unsaturated linear hydrocarbon group having 13 to 17 carbon atoms; [4] The emulsifier for emulsion polymerization according to any one of the above [1] to [3], wherein A is an ethylene group; [5] The emulsifier for emulsion polymerization according to any one of the above [1] to [4], wherein n is 5 to 60; [6]Q + is a sodium ion, a potassium ion, or an ammonium ion; [7] A resin emulsion comprising an emulsion polymer of a composition comprising the emulsifier for emulsion polymerization according to any one of the above [1] to [6], a polymerizable monomer, and water; [8] The resin emulsion according to [7] above, which is used in paints, adhesives, film coating agents, impregnation agents, or fiber processing agents. [Example]

[0055] The effects of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following description, "parts" means parts by mass, and "%" means % by mass. In the following examples, unless otherwise specified, operations were performed at 25°C.

[0056] [Production of the compound represented by formula (1)] [Manufacturing Example 1] Synthesis of hydrogenated cardanol 9-mol ethylene oxide adduct An autoclave was charged with 400 g of hydrogenated cardanol (manufactured by Cardolite, trade name: NC-510-HP) and 1.91 g of a 48 mass % aqueous potassium hydroxide solution. The atmosphere in the system was then replaced with nitrogen, and 518.8 g of ethylene oxide was then injected at approximately 150°C and 0.5 MPa or less, and the reaction was carried out at the same temperature for an additional hour. After cooling the system, the resulting reaction solution was neutralized with 1.83 g of acetic acid to obtain a hydrogenated cardanol-ethylene oxide 9 mole adduct.

[0057] [Manufacturing Example 2] Synthesis of Compound 2 (ammonium sulfate salt of hydrogenated cardanol ethylene oxide 9-mol adduct) A four-neck flask was charged with 200 g of the hydrogenated cardanol-ethylene oxide 9-mol adduct obtained in Production Example 1, and the temperature was raised to 135°C. 26.4 g of sulfamic acid was added and reacted for 2 hours. After cooling, the resulting reaction liquid was neutralized with a 25% by mass aqueous ammonia solution to obtain Compound 2 (ammonium sulfate salt of hydrogenated cardanol-ethylene oxide 9-mol adduct).

[0058] [Manufacturing Example 3] Synthesis of Compound 4 (Sodium Sulfate of Hydrogenated Cardanol with 9-Mole Ethylene Oxide Adduct) A four-neck flask was charged with 70.84 g of compound 2 (ammonium sulfate salt of hydrogenated cardanol-ethylene oxide 9-mol adduct) obtained in Production Example 2 and 3.10 g of sodium hydroxide, and counter ion exchange was carried out to obtain compound 4 (sodium sulfate salt of hydrogenated cardanol-ethylene oxide 9-mol adduct).

[0059] [Manufacturing Example 4] Synthesis of Compound 1 (ammonium sulfate salt of unsaturated cardanol ethylene oxide 9-mol adduct) Compound 1 (ammonium sulfate salt of unsaturated cardanol ethylene oxide 9-mol adduct) was obtained in the same manner as in Production Example 2, except that the hydrogenated cardanol ethylene oxide 9-mol adduct in Production Example 2 was changed to an unsaturated cardanol ethylene oxide 9-mol adduct (manufactured by Cardolite, trade name: GX-5167).

[0060] [Manufacturing Example 5] Synthesis of Compound 3 (Sodium Sulfate of Unsaturated Cardanol Ethylene Oxide 9-Mole Adduct) Compound 3 (sodium sulfate of unsaturated cardanol-ethylene oxide 9-mol adduct) was obtained in the same manner as in Production Example 3, except that the raw material in Production Example 3 was changed to Compound 1 (ammonium sulfate of unsaturated cardanol-ethylene oxide 9-mol adduct) obtained in Production Example 4.

[0061] [Manufacturing Example 6] Synthesis of Compound 5 (Polyoxyethylene Nonylphenyl Ether Sulfate Sodium Salt) Compound 5 (polyoxyethylene nonylphenyl ether sulfate sodium salt) was obtained in the same manner as in Production Example 3, except that the raw material was changed to 70.86 g of Newcol 564SF and the amount of sodium hydroxide charged was changed to 4.20 g.

[0062] [Manufacturing Example 7] Compound 6 (Polyoxyethylene alkyl ether sulfate sodium salt) Compound 6 (polyoxyethylene alkyl ether sulfate sodium salt) was obtained in the same manner as in Production Example 3, except that the raw material was changed to 70.50 g of Newcol 2308SF and the amount of sodium hydroxide charged was changed to 4.46 g.

[0063] [Manufacturing resin emulsion] Resin emulsions were produced using the compounds 1 to 4 obtained above as emulsifiers for emulsion polymerization. As comparative examples, resin emulsions were produced using the following compounds as emulsifiers for emulsion polymerization.

[0064] Comparative Example Emulsifier for Emulsion Polymerization (Emulsifier for emulsion polymerization of ammonium salts) Nucol (registered trademark, hereafter omitted) 564SF (manufactured by Nippon Nyukazai Co., Ltd.) …Polyoxyethylene nonylphenyl ether sulfate ammonium salt Newcol 707SF (manufactured by Nippon Nyukazai Co., Ltd.) …Polyoxyethylene polycyclic phenyl ether sulfate ammonium salt Newcol 2308SF (manufactured by Nippon Nyukazai Co., Ltd.) …Polyoxyethylene alkyl ether sulfate ammonium salt (Sodium salt emulsifier for emulsion polymerization) ·Compound 5 ...Polyoxyethylene nonylphenyl ether sulfate sodium salt Newcol 707SN (manufactured by Nippon Nyukazai Co., Ltd.) ...Polyoxyethylene polycyclic phenyl ether sulfate sodium salt ·Compound 6 ...Polyoxyethylene alkyl ether sulfate sodium salt.

[0065] <<Emulsifiers for emulsion polymerization of examples>>

[0066] [ka]

[0067] Example 1 A 500 mL polyethylene container was charged with a monomer / water / surfactant mixture, which consisted of butyl acrylate (70.00 parts by mass), methyl methacrylate (100.00 parts by mass), styrene (30.00 parts by mass), acrylic acid (4.00 parts by mass), Compound 1 (3.80 parts by mass), a 10% aqueous solution of ammonium peroxodisulfate (5.00 parts by mass), and pure water (95.13 parts by mass).

[0068] Using a homogenizer (TKROBOMICS manufactured by PRIMIX), the monomer / water / surfactant mixture was pre-stirred at approximately 1400 rpm. After confirming emulsification, the stirring speed was increased to 4000 rpm and stirred for 2 minutes to prepare a pre-emulsion.

[0069] In a 500 mL separable flask, pure water (82.63 parts by mass) and Compound 1 (0.20 parts by mass) were charged as an emulsifier solution.

[0070] The 500 mL separable flask containing the emulsifier solution was immersed in a water bath and heated to 83°C over 20 minutes, and a 10% aqueous solution of ammonium peroxodisulfate (5.00 parts by mass) was added to the emulsifier solution. The pre-emulsion obtained above was then added dropwise to the solution. After the entire amount of the pre-emulsion was added dropwise over 2 hours, the mixture was aged at 83°C for 2 hours to promote the reaction of the remaining monomers.

[0071] The resulting reaction solution was cooled to room temperature over 30 minutes. Then, aqueous ammonia was added to the reaction solution to adjust the pH to about 8.0, and then pure water was added to adjust the solid content to 40.5% by mass. The aggregates in the reaction solution were then removed by filtration using a nylon mesh with a mesh size of 200 μm, yielding the resin emulsion of Example 1.

[0072] <Example 2> A resin emulsion of Example 2 was obtained in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1.

[0073] Example 3 A resin emulsion of Example 3 was obtained in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1.

[0074] Example 4 A resin emulsion of Example 4 was obtained in the same manner as in Example 1, except that Compound 4 was used instead of Compound 1.

[0075] <Comparative Example 1> A resin emulsion of Comparative Example 1 was obtained in the same manner as in Example 1, except that Newcol 564SF (ammonium salt) was used instead of Compound 1.

[0076] <Comparative Example 2> A resin emulsion of Comparative Example 2 was obtained in the same manner as in Example 1, except that Newcol 707SF (ammonium salt) was used instead of Compound 1.

[0077] <Comparative Example 3> A resin emulsion of Comparative Example 3 was obtained in the same manner as in Example 1, except that Newcol 2308SF (ammonium salt) was used instead of Compound 1.

[0078] <Comparative Example 4> A resin emulsion of Comparative Example 4 was obtained in the same manner as in Example 1, except that Compound 5 (sodium salt of Newcol 564SF) was used instead of Compound 1.

[0079] <Comparative Example 5> A resin emulsion of Comparative Example 5 was obtained in the same manner as in Example 1, except that Newcol 707SN (sodium salt) was used instead of Compound 1.

[0080] <Comparative Example 6> A resin emulsion of Comparative Example 6 was obtained in the same manner as in Example 1, except that Compound 6 (sodium salt of Newcol 2308SF) was used instead of Compound 1.

[0081] [Polymerization conversion rate] One part by mass of the resin emulsion obtained above was weighed and dried at 110±5°C for 2 hours to obtain a resin emulsion solid content. The obtained resin emulsion solid content was divided by the mass of the resin emulsion before drying (1 part by mass) to calculate the "solid content concentration (mass%) after polymerization." In addition, the total mass of the solid content of each raw material relative to the total mass of each raw material was calculated as the "solid content concentration (mass%) at the time of raw material charging." The polymerization conversion rate was calculated using the obtained solid content concentration according to the following formula.

[0082] Polymerization conversion rate (%) = solids concentration after polymerization / solids concentration at the time of raw material charging × 100.

[0083] [Particle size] The average particle size of the particles in the resin emulsion was measured by dynamic light scattering using a Malvern particle size analyzer, Zetasizer Nano ZS.

[0084] [Foaming property] Foaming properties of emulsifiers for emulsion polymerization (Ross Miles method) A 1% by mass aqueous solution of each of the compounds 1 to 4 obtained above and the emulsifier for emulsion polymerization used as a comparative example was prepared as a sample solution in a 1-L plastic container. Water at 25°C was circulated through the measuring device to maintain a constant temperature, and 50 mL of the sample solution was added without creating bubbles. 200 mL of the sample solution was added dropwise in one go, and the foam height was measured twice, immediately after the entire amount was added and again 5 minutes later, and the average value was calculated.

[0085] Foaming properties of resin emulsion (shaking method) 100 mL of a 10% diluted resin emulsion sample was placed in a 250 mL measuring cylinder. The cylinder was then covered and turned upside down 10 times, and the foam height was measured immediately after and 5 minutes later.

[0086] <Coating film test> [Coating film production] The resin emulsion was placed on a black acrylic plate (150 mm × 70 mm × 2 mm) as a substrate, and a thin film (dry film thickness 14.8 μm) was applied using a bar coater (No. 16) (manufactured by RDS, product name: stainless steel rod coated wire bar).

[0087] The acrylic plate on which the thin film was formed was pre-dried at room temperature for 1 minute, and then dried in a thermostatic chamber at 80°C for 30 minutes.Then, it was left to stand and cure for 48 hours in an environment of 25°C and 50% RH to obtain a test coating film.

[0088] Glossiness The gloss of the resulting coating film at 60° was measured using a gloss meter 1G-331 (manufactured by Horiba, Ltd.) The measurement results are shown in Table 2.

[0089] [Adhesion] The resulting coating film was subjected to a cross-cut test according to the following procedure, and evaluated according to the following criteria.

[0090] (1) On the surface where the coating film is formed (coating surface), make 11 parallel cuts at 1 mm intervals that reach the substrate, then turn the surface 90° and make 11 more cuts in the same way; (2) Apply cellophane adhesive tape so that it adheres to the incised surface of the coating film approximately 50 mm thick, and rub it with an eraser to adhere the tape to the coating film; (3) After applying the tape, wait 1-2 minutes, then hold the edge of the tape perpendicular to the coating surface and peel it off; (4) On the coating surface where the cellophane adhesive tape was peeled off, the number of lattices that were not peeled off and the number of lattices that were peeled off out of 100 lattices were counted, and this is shown in Table 2 as "Number of lattices that were not peeled off / Total number of lattices (100)." If there are 100 lattices that were not peeled off out of 100 lattices, the test is considered to have passed.

[0091] [Chemical resistance] ·Acid resistance 2 mL of a 3% by mass H2SO4 aqueous solution was dropped onto the coating film and allowed to stand. After 4 hours, the chemical was wiped off and the coating film was visually inspected for discoloration and evaluated according to the following evaluation criteria.

[0092] Alkali resistance 2 mL of a 1% by mass NaOH aqueous solution was dropped onto the coating film and allowed to stand. After 4 hours, the chemical was wiped off and the coating film was visually inspected for discoloration and evaluated according to the following evaluation criteria.

[0093] Evaluation criteria ○: No change in the coating ×: The coating film turns white or the coating film surface dissolves and cannot be restored.

[0094] [Table 1]

[0095] [Table 2]

[0096] The results shown in Table 1 demonstrate that good emulsion polymerization is possible by using compounds 1 to 4 of the examples as emulsifiers for emulsion polymerization. Furthermore, compounds 1 to 4 of the examples have excellent low-foaming properties, and it is also evident that resin emulsions obtained using compounds 1 to 4 of the examples have low-foaming properties.

[0097] Furthermore, the results shown in Table 2 show that the coating films made of the resin emulsions obtained by using the compounds 1 to 4 of the examples as emulsifiers for emulsion polymerization have remarkably excellent acid resistance.

Claims

1. The following formula (1): 【Chemical 1】 In formula (1), R １ represents a saturated or unsaturated hydrocarbon group having 13 to 17 carbon atoms, A represents a linear or branched alkylene group having 2 to 4 carbon atoms; n represents the average number of moles of oxyalkylene groups added represented by AO, and is a number from 1 to 80; m is Q ＋ represents a valence of 1 or 2, Q ＋ represents an alkali metal cation, an alkaline earth metal cation, or a nitrogen-containing compound cation, An emulsifier for emulsion polymerization, comprising a compound represented by the formula:

2. 2. The emulsifier for emulsion polymerization according to claim 1, wherein the compound is a compound derived from cardanol.

3. R １ The emulsifier for emulsion polymerization according to claim 1 or 2, wherein is a saturated or unsaturated linear hydrocarbon group having 13 to 17 carbon atoms.

4. 3. The emulsifier for emulsion polymerization according to claim 1, wherein A is an ethylene group.

5. The emulsifier for emulsion polymerization according to claim 1 or 2, wherein n is 5 to 60.

6. Q ＋ 3. The emulsifier for emulsion polymerization according to claim 1, wherein is a sodium ion, a potassium ion, or an ammonium ion.

7. A resin emulsion comprising an emulsion polymer of a composition comprising the emulsifier for emulsion polymerization according to claim 1 or 2, a polymerizable monomer, and water.

8. The resin emulsion according to claim 7, which is used in paints, adhesives, film coating agents, impregnation agents, or fiber processing agents.

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