JP7097604B2 - Defoamer - Google Patents

Description

The present invention relates to an antifoaming agent.

"A hydrophobic silica dispersion (A) containing a hydrophobic silica (A1) and a hydrocarbon oil (A2) having a flow point of -50 to 2 ° C., a polyoxyalkylene compound (B) and a polyoxyalkylene poly. A defoaming agent containing a hydrocarbon fatty acid ester (C) is known (Patent Document 1).

Japanese Patent No. 4899004

When a conventional defoaming agent is applied to a paint for forming a coating film that requires high gloss, there is a problem that a high gloss coating film may not be obtained. Therefore, an object of the present invention is to provide an antifoaming agent that can easily obtain a high-gloss coating film (that is, has excellent glossiness).

The characteristics of the defoaming agent of the present invention are the polymer (A) having the (meth) acrylate represented by the formula (1) as a constituent unit, or the (meth) acrylate and the (meth) acrylic represented by the formula (1). The constituent unit is an acid, another monomer selected from (meth) acrylic acid alkyl ester, styrene, acrylonitrile and maleic acid, and the content of the other monomer unit is represented by the formula (1) (meth). ) The copolymer (A) and the nonionic activator (B) which are 1 to 9% by weight based on the weight of the acrylate unit are contained, and the nonionic activator (B) is represented by the formula (2). The gist is that the weight ratio (A: B) of the (co) polymer (A) to the nonionic activator (B) is 1:99 to 40:60 .

M- (OA) _n R ¹ (1)

Ｒ ^２ は炭素数１～３０のモノオール又は４～８価の糖類の反応残基、Ｒ ^３ は炭素数１～２５の有機基、ＯＡは炭素数２～４のオキシアルキレン基｛（ＯＡ） _ｍ は複数種類のＯＡから構成されてもよい｝、ｍは０～１００の整数で一分子中に複数のｍが存在する場合、それぞれ同じでも異なっていてもよく、ｐは０、１又は４～８の整数、ｑは０、１又は４～８の整数、ｐ及びｑの合計は１又は４～８である。但し、少なくとも１つのｍが０の場合、ｐは１又は４～８の整数、ｑは０又は３～７の整数である。 M is a (meth) acryloyloxy group, OA is an oxyalkylene group having 2 to 4 carbon atoms {(OA) _n may be composed of a plurality of types of OA}, n is an integer of 1 to 40, and R ¹ is carbon. It is any one hydrocarbon group selected from an alkyl group having 7 to 24 carbon atoms, an alkenyl group having 7 to 23 carbon atoms, or an aryl group having 7 to 15 carbon atoms.

R ² is a reaction residue of a monool having 1 to 30 carbon atoms or a saccharide having 4 to 8 valences, R ³ is an organic group having 1 to 25 carbon atoms, and OA is an oxyalkylene group having 2 to 4 carbon atoms {(OA). _m may be composed of a plurality of types of OA}, m is an integer of 0 to 100, and when a plurality of m exists in one molecule, they may be the same or different, and p is 0, 1, or 4. An integer of -8, q is an integer of 0, 1 or 4-8, and the sum of p and q is 1 or 4-8. However, when at least one m is 0, p is an integer of 1 or 4 to 8, and q is an integer of 0 or 3 to 7.

The gist of the water-based coating composition of the present invention is that it comprises a water-based coating material and the above-mentioned defoaming agent.

When the defoaming agent of the present invention is applied to a paint for forming a coating film requiring high gloss, a high gloss coating film can be easily obtained (that is, excellent glossiness).

The water-based coating composition of the present invention can easily obtain a high-gloss coating film (that is, has excellent glossiness).

"(Meta) acrylate" means "acrylate" or "methacrylate", "(meth) acryloyloxy group" means "acryloyloxy group" or "methacryloyloxy group", and "(meth) acrylic acid" It means "acrylic acid" or "methacrylic acid", and "(co) polymer" means "polymer" or "polymer" (these may be simply referred to as "polymer"). ..

<(Co) polymer (A) containing (meth) acrylate represented by formula (1) as an essential constituent monomer>
The oxyalkylene group (OA) having 2 to 4 carbon atoms includes oxyethylene, oxypropylene and oxybutylene. Of these, from the viewpoint of glossiness, oxyethylene and a mixture of oxyethylene and oxypropylene are preferable.

When a plurality of types of oxyalkylene groups (OA) are contained in (OA) n, the bonding order (block-shaped, random-shaped and combinations thereof) and the content ratio of these oxyalkylene groups (OA) are not limited. It is preferable to include a block shape or a combination of a block shape and a random shape, and more preferably, a block shape is included.

When the oxyalkylene group contains oxyethylene, the content ratio (mol%) of oxyethylene is preferably 10 to 90 or 100, more preferably 20 to 75 or 100, particularly more preferably 20 to 75 or 100, based on the total number of moles of the oxyalkylene group. It is preferably 50 to 65 or 100.

n is preferably an integer of 1 to 40, more preferably an integer of 2 to 35, and particularly preferably 4 to 30. Within this range, the defoaming property and the glossiness are further improved.

Alkyl having 7 to 24 carbon atoms among any one hydrocarbon group (R ¹ ) selected from an alkyl group having 7 to 24 carbon atoms, an alkenyl group having 7 to 23 carbon atoms, or an aryl group having 7 to 15 carbon atoms. Examples of the group include heptyl, 2-ethylheptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, heptadecyl, isoheptadecyl, octadecyl, icosyl, henicosyl, trichosyl and tetracosyl.

Among the hydrocarbon groups (R ¹ ), the alkenyl groups having 7 to 23 carbon atoms include heptenyl, 2-ethylheptenyl, octenyl, nonenyl, decenyl, undecenyl, tridecenyl, heptadecenyl, octadecenyl, isoheptadecenyl, nonacosenyl and henicosenyl. And trichosenyl and the like.

Among the hydrocarbon groups (R ¹ ), examples of the aryl group having 7 to 15 carbon atoms include benzyl, p-ethylphenyl, p-butylphenyl, p-heptylphenyl, p-nonylphenyl and p-cumylphenyl. ..

Among these hydrocarbon groups (R ¹ ), an alkyl group having 8 to 20 carbon atoms and an alkenyl group having 8 to 20 carbon atoms are preferable, and decyl, undecyl, dodecyl, tridecyl, pentadecyl, octadecyl and octadecenyl are more preferable. ..

The (co) polymer (A) can be composed of other monomers other than the (meth) acrylate represented by the formula (1). The other monomer is not limited as long as it can be copolymerized with the (meth) acrylate represented by the formula (1), and is limited to (meth) acrylic acid and (meth) acrylic acid alkyl ester {(meth) acrylic. Methyl acid and ethyl (meth) acrylate}, polyoxyalkylene glycol di (meth) acrylate, tri (meth) acrylate of trimerirol propanealkylene oxide adduct, and other vinyl monomers {styrene, α-methylstyrene, t-butylstyrene, chlorostyrene, acrylonitrile, maleic acid, etc.} and the like.

When another monomer is used as a constituent unit, the other monomer is preferably a (meth) acrylate having a polyoxyalkylene chain, more preferably a polyoxyalkylene glycol di (meth) acrylate, and particularly preferably poly. Oxyethylene glycol di (meth) acrylate (the number of repetitions of oxyethylene is preferably 3 to 14, and more preferably 4 to 9).

When another monomer is contained as a constituent monomer, the content (% by weight) of the other monomer unit is 1 to 1 based on the weight of the (meth) acrylate unit represented by the formula (1). 9 is preferable, and 1 to 4 is more preferable. Within this range, the defoaming property and the glossiness are further improved.

The weight average molecular weight (Mw) of the (co) polymer (A) is preferably 800 to 60,000, more preferably 4,000 to 40,000. Within this range, the defoaming property and the glossiness are further improved.

The weight average molecular weight (Mw) is measured by a gel permeation chromatography (GPC) method using polyethylene glycol having a known molecular weight as a standard substance (column temperature: 40 ° C., eluent: tetrahydrofuran, flow velocity: 0.5 ml / min). , Sample concentration: 0.1 wt% eluent solution.).

The (co) polymer (A) can be easily obtained by a known method (radical polymerization reaction, transesterification reaction, etc.). For example, the (co) polymer (A) can be obtained by a known polymerization method using the (meth) acrylate represented by the formula (1) as an essential constituent monomer. Further, it is composed of (meth) acrylic acid alkyl ester by a known polymerization method using (meth) acrylic acid alkyl ester {(meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, etc.} as an essential constituent monomer (. After preparing the co) polymer, this (co) polymer and HO- (OA) _n R ¹ {OA, n, R ¹ are the same as in the formula (1), and HO represents a hydroxyl group. } Can also be obtained by a transesterification reaction (known method or the like) with the compound represented by.

The (meth) acrylate represented by the formula (1) can be easily obtained from the market, and for example, Blemmer 50 POEO-800B {M: methacryloyloxy, (OA) n: 8 mol of oxyethylene / 4 mol of oxypropylene, R ¹ : 2-Ethylheptyl}, Blemmer PLE-200 {M: Methacryloyloxy, (OA) n: 4 mol of oxyethylene, ^R1 : Dodecyl}, Blemmer PLE-1300 {M: Methacyoyloxy, (OA) n: 30 mol of oxyethylene, R ¹ : dodecyl}, Blemmer PSE-1300 {M: methacryloyloxy, (OA) n: 3 mol of oxyethylene, R ¹ : octadecyl}, Blemmer ALE-200 {M: acryloyloxy, (OA) n: 4 mol of oxyethylene, R ¹ : dodecyl} and Blemmer ANP-300 {M: acryloyloxy, (OA) n: 5 mol of oxypropylene, R ¹ : nonylphenyl} (above, Nichiyu Co., Ltd., "Blemmer" Is a registered trademark of the same company.)}, And Aronix M-110 {M: Acryloyloxy, (OA) n: 1 mol of oxyethylene, ^R1 : p-phenylisopropylphenyl} and Aronix M-120 {M: Acryloyl. Oxy, (OA) n: 2 mol of oxyethylene, R ¹ : 2-ethylhexyl} (above, Toa Synthetic Co., Ltd., "Aronix" is a registered trademark of the company) and the like. The inside of {} corresponds to the equation (1), the total number of moles corresponds to n, and "/" represents a block shape.

<Nonion activator (B)>

R ² is a reaction residue of an active hydrogen compound having 1 to 30 carbon atoms and 1 to 12 valences, R ³ is an organic group having 1 to 25 carbon atoms, and OA is an oxyalkylene group having 2 to 4 carbon atoms {(OA) _m . May be composed of multiple types of OA}, m is an integer of 0 to 100, and when multiple m are present in one molecule, they may be the same or different, and p is an integer of 0 to 12. q is an integer of 0 to 12, and the sum of p and q is 1 to 12. However, when at least one m is 0, p is an integer of 1 to 12, and q is an integer of 0 to 11.

The oxyalkylene group (OA) having 2 to 4 carbon atoms includes oxyethylene, oxypropylene and oxybutylene. Of these, from the viewpoint of defoaming property, oxypropylene and a mixture of oxyethylene and oxypropylene are preferable.

When multiple types of oxyalkylene groups are contained in OA, the bonding order (block-like, random-like and combinations thereof) and content ratio of these oxyalkylene groups are not limited, but may be block-like or block-like and random-like. It is preferable to include the combination of the above, and more preferably, it contains a block shape.

When the oxyalkylene group contains oxypropylene, the content ratio (mol%) of oxypropylene is preferably 10 to 90 or 100, more preferably 20 to 75 or 100, particularly more preferably 20 to 75 or 100, based on the total number of moles of the oxyalkylene group. It is preferably 50 to 65 or 100.

m is preferably an integer of 0 to 100, more preferably an integer of 2 to 50, and particularly preferably 4 to 40. Within this range, the defoaming property is further improved.

Examples of the active hydrogen compound capable of constituting the reaction residue (R ² ) of the active hydrogen compound having 1 to 30 carbon atoms and 1 to 12 valences include alcohol, carboxylic acid, amine, hydroxycarboxylic acid and phenol.

Alcohols include monool (methanol, propanol, t-butanol, 2-ethylhexanol, dodecanol, octadecanol, etc.) and diols (ethylene glycol, isopropylene glycol, 1,4-butylene glycol, 1,5-pentyl glycol). , 1,6-Hexane glycol and neopentyl glycol, etc.), Triol (glycerin, butanetriol, trimethylolpropane, etc.), 4-valent or higher polyols (pentaerythritol, sorbitol, sorbitan, saccharides (monosaccharides such as fructose, sho) Disaccharides such as sugar) and condensates such as triol can be mentioned.

Carboxylic acids include monocarboxylic acids (acetic acid, butylic acid, lauric acid, stearic acid, etc.), dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutanic acid, adipic acid, fumaric acid, maleic acid, phthalic acid, etc.), 3. Examples thereof include polyvalent carboxylic acids having a valence or higher (cyclohexanetetracarboxylic acid, trimellitic acid, ethylenetetracarboxylic acid, benzenetetracarboxylic acid and the like.

Examples of the amine include monoamine (ethylamine, isopropylamine, etc.), diamine (ethylenediamine, propylenediamine, etc.), triamine (diethylenetriamine, etc.), tetramine (butane-1,1,4,4-tetraamine, etc.) and the like. In addition to these, ethanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.) can also be used.

Examples of the hydroxycarboxylic acid include lactic acid, malic acid and citric acid.

Examples of the phenol include phenol, cresol, naphthol, catechol, resorcinol, hydroquinone, pyroganol, phloroglucinol, hexahydroxybenzene and the like.

Of the reaction residues (R ² ) of the active hydrogen compound having 1 to 30 carbon atoms and 1 to 12 valences, the reaction residue of alcohol and the reaction residue of carboxylic acid are preferable, and more preferably the reaction residue of alcohol. ..

Examples of the organic group (R ³ ) having 1 to 25 carbon atoms include an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 4 to 25 carbon atoms, an acyl group having 2 to 25 carbon atoms, and an aryl group having 7 to 25 carbon atoms. included.

Examples of the alkyl group having 1 to 25 carbon atoms include methyl, ethyl, isopropyl, butyl and hexyl, in addition to the alkyl group having 7 to 24 carbon atoms of ^R1 .

Examples of the alkenyl group having 4 to 25 carbon atoms include propenyl, butenyl, hexenyl and the like, in addition to the alkenyl group having 7 to 23 carbon atoms of ^R1 .

Acetyl groups having 2 to 25 carbon atoms include acetyl, propionyl, butanoyl, hexanoyl, heptanoyle, octanoyl, decanoyle, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, eikosanoyl, henikosanoyl, docosanoyl, trichosanoyl, tetra. , Pentacosanoyl, butenoyl, butazienoyl, hexenoyl, octenoyl, decenoyl, dodecenoyl, tetradecenoyl, cyclohexanoyl, methylcyclohexanoyl, methylcyclohexenoyl and the like.

The aryl group having 7 to 25 carbon atoms includes p-decylphenyl, p-dodecylphenyl, p-undecylphenyl, p-tetradecylphenyl, and p-hexa, in addition to the aryl group having 7 to 15 carbon atoms of ^R1 . Examples thereof include decylphenyl and p-octadecylphenyl.

Of the organic groups (R3) having ¹ to 25 carbon atoms, an alkyl group, an alkenyl group and an acyl group are preferable, and an alkyl group and an acyl group are more preferable, and an acyl group is particularly preferable.

The compound represented by the formula (2) can be easily obtained from the market, and is easily available from the market. , "Ionet" is a registered trademark of the company), Emulgen series, Leodor series (Kaou Co., Ltd., "Emalgen", "Leodor" are registered trademarks of the company) and the like.

The weight ratio of the (co) polymer (A) to the nonionic activator (B) is preferably 1:99 to 40:60, more preferably 3:97 to 25:75. Within this range, the defoaming property and the glossiness are further improved.

The defoaming agent of the present invention preferably further contains silicone (C).
Silicone (C) includes dimethyl silicone (C1) and modified silicone (C2).

Examples of the dimethyl silicone (C1) include dimethyl silicone having a kinematic viscosity of 1 to 10,000 (mm ² / s, 25 ° C.), and cyclodimethyl silicone such as cyclooctamethyltetrasiloxane is also included.

As the modified silicone (C2), a part of the methyl group of the dimethyl silicone (C1) is a polyether chain, an alkyl group, an alkoxy group, a phenyl group, a hydrogen atom, a halogen (chlorine, bromine, etc.) atom and / or an aminoalkyl group. Etc. are included.

As the modified silicone (C2), those having a kinematic viscosity (25 ° C.) of 1 to 10,000 mm ² / s and an HLB of 0 to 6 (preferably 2 to 5) can be used.

HLB is a concept that expresses the balance between hydrophilic and hydrophobic groups in a molecule, and the HLB value of modified silicone is "the properties and applications of surfactants" (author Takao Karigome, publisher Koshobo Co., Ltd., It can be calculated as follows using the "HLB measurement method by emulsification test" described on pages 89 to 90 of (issued on September 1, 1980).

<Measurement method of HLB by emulsification test of modified silicone>
The modified silicone (γ) whose HLB is unknown and the emulsifier (α) whose HLB is known are mixed in different ratios to emulsify the oil agent (β) whose HLB is known. The HLBγ of the modified silicone (γ) is calculated from the mixing ratio when the thickness of the emulsified layer is maximized using the following formula.

HLBγ = {(HLBβ) × (Wα + Wγ)-(Wα × HLBα)} ÷ Wγ

Wα is the weight fraction of the emulsifier (α) based on the total weight of the modified silicone (γ) and the emulsifier (α), and Wγ is the weight of the modified silicone (γ) based on the total weight of the modified silicone (γ) and the emulsifier (α). The fraction, HLBα is HLB of emulsifier (α), HLBβ is HLB of oil (β), and HLBγ is HLB of modified silicone (γ).

Examples of the modified silicone (C2) are easily available from the market, and examples thereof include the following products.
<Polyester modified silicone>
FZ-2110 (HLB = 0), FZ-2164 (HLB = 5), FZ-2191 (HLB = 6), FZ-5609 (HLB = 4), FZ-7001 (HLB = 5), SF8410 (HLB = 6) ), Y-7006 (HLB = 2), FZ-2203 (HLB = 2), FZ-2222 (HLB = 4) (Toray Dow Corning Co., Ltd.), KF-745 (HLB = 4), KF-6020 ( HLB = 4), X-22-4515 (HLB = 5), KF-6015 (HLB = 5), KF-6017 (HLB = 5) (Shin-Etsu Chemical Co., Ltd.)

<Alkyl modified silicone (HLB = 0)>
580WAX, BY16-868, BY16-606, OXF-0203, OXF-0230, SF8416, SF9419, SF8422 (Toray Dow Corning Co., Ltd.), KF-421, KF413, KF-414, KF-415, KF-4003, KF-4701, KF-4917, KF-7235B, X-22-7322 (Shin-Etsu Chemical Co., Ltd.)

<Alkoxy modified silicone (HLB = 0)>
FZ-3704 (Toray Dow Corning Co., Ltd.)

<Phenyl-modified silicone (HLB = 0)>
SH510, SH550, SH710 (Toray Dow Corning Co., Ltd.), KF-50, KF-53, KF-54, X-21-3265, KF-54SS (Shin-Etsu Chemical Co., Ltd.)

Of the silicones (C), the modified silicone (C2) is preferable, and the polyether-modified silicone is more preferable.

When the silicone (C) is contained, the content (parts by weight) of the silicone (C) is preferably 1 to 100 based on 100 parts by weight of the total of the (co) polymer (A) and the nonionic activator (B). , More preferably 2 to 50, and particularly preferably 3 to 33. Within this range, the defoaming property and the glossiness are further improved.

The defoaming property of the present invention preferably does not contain the hydrophobic compound (D), but can be contained within a range that does not affect the gloss of the coating film. Hydrophobic compound (D) includes mineral oils, animal and vegetable oils and synthetic lubricating oils.

Examples of the mineral oil include known mineral oils, such as spindle oils, machine oils and refrigerating machine oils. Animal and vegetable oils include known animal and vegetable oils, such as fish oil, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil, rice bran oil, corn oil, safflower oil, olive oil, sesame oil, evening primrose oil, palm oil, and shea butter. , Salfice, cacao butter, palm oil, palm kernel oil and the like. Examples of the synthetic lubricating oil include known synthetic lubricating oils, and examples thereof include polyolefin oil (α-olefin oil), polyglycol oil, polybutene oil, alkylbenzene oil (alkhet oil), and isoparaffin oil.

When the hydrophobic compound (D) is contained, the content of the hydrophobic compound (D) is 1 to 100 parts by weight based on 100 parts by weight of the total of the (co) polymer (A) and the nonionic activator (B). The amount is preferably 2 to 50 parts by weight, more preferably 3 to 33 parts by weight. Within this range, the gloss of the coating film is less adversely affected.

The defoaming agent of the present invention may contain a thickener, a dispersant, a preservative and / or an antifreeze agent.

Thickeners include Zantan gum, locust bean gum, guar gum, carrageenan, alginic acid and its salts, tragant gum, magnesium aluminum silicate, bentonite, synthetic hydrous silicic acid, and synthetic polymer thickeners containing carboxyl groups (as a trade name). For example, SN thickener 636, SN thickener 641; Sannopco Co., Ltd.), an association-type thickener containing a polyoxyethylene chain (for example, SN thickener 625N, SN thickener 665T; Sannopco Co., Ltd.) and the like can be mentioned.

Examples of the dispersant include polyacrylic acid (salt), partially saponified polyvinyl alcohol, and sulfated polyvinyl alcohol.

As the preservative, known preservatives (Dictionary of antibacterial and antifungal agents, Japan Antibacterial and Antifungal Society, 1st edition, 1986, pp. 1-32, etc.) can be used, and formalin and 5-chloro-2 can be used. -Methyl-4-isothiazolin-3-one and the like can be mentioned.

Examples of the antifreeze agent include ethylene glycol, propylene glycol and glycerin.

The defoaming agent of the present invention may be used as it is, diluted with a solvent, water, an aqueous solution or the like, or may be supported on a powder such as silica or calcium carbonate before use.

As the solvent, known solvents (solvent handbook, published by Kodansha, 1976, pp. 143-881, etc.) can be used, and examples thereof include butyl cellosolve, propylene glycol monopropyl ether, and 1-butanol.

The defoaming agent of the present invention is a defoaming agent for paints, a defoaming agent for cement building materials (concrete, mortar, plaster, etc.) and for various manufacturing processes (paper making process, fermentation process, wastewater treatment process, monomer stripping process and polymer. Polymerization process, etc.) Can be applied as an antifoaming agent, etc. Among these, it is suitable as a defoaming agent for paints and a defoaming agent for building materials, and further suitable as a defoaming agent for water-based coating materials.

Suitable water-based coating materials include coating materials containing acrylic binders, vinyl acetate binders, styrene binders, halogenated olefin binders, urethane binders, acrylic-silicone binders or fluorine binders.

When the defoaming agent of the present invention is applied to a paint, examples of the defoaming agent of the present invention include (1) a method of adding the defoaming agent at the time of pigment dispersion and / or (2) a method of adding the defoaming agent after the paint is prepared. When applied to various manufacturing processes, the defoaming agent of the present invention is added to (1) the supply of raw materials, (2) before heating and / or depressurization, and / or (3) the final finishing process and the like. Any method may be used.

The amount of the defoaming agent added of the present invention can be appropriately determined depending on the application target, application, etc. For example, when the defoaming agent of the present invention is used as a defoaming agent for a water-based coating material, the defoaming agent of the present invention The content (% by weight) is preferably 0.05 to 5, more preferably 0.1 to 4.5, particularly preferably 0.2 to 4, and most preferably 0., based on the weight of the water-based coating material. It is 3 to 3. Within this range, the defoaming property and the suppression of the decrease in gloss are further improved.

A water-based coating composition comprising a water-based coating material and the above-mentioned defoaming agent can be easily prepared by a known method.
The water-based coating composition comprising the defoaming agent and the water-based coating material of the present invention can be applied to the object to be coated by a usual method, and can be applied with a brush coating, a roller coating, an air spray coating, an airless coating, a roll coater coating and a flow. A coating method such as coater coating can be applied, but the effect is particularly remarkable during brush coating and roller coating.

Unless otherwise specified, parts mean parts by weight and% means% by weight. The weight average molecular weight (Mw) was measured under the following conditions.

Model: HLC-8320GPC EcoSEC (Tosoh Corporation)
Column: TSK gel SuperHZ4000 (Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Solvent: Tetrahydrofuran Flow rate: 0.500 mL / min
Sample concentration: 0.1%
Injection volume: 20 μL
Standard: Polyoxyethylene glycol (Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE)
Data processing device: GPC workstation EcoSEC-WS (Tosoh Corporation)

<Manufacturing example 1>
After putting 40 parts of methyl ethyl ketone into a pressure resistant reaction vessel capable of stirring, heating, cooling, dropping, nitrogen substitution, pressurization with nitrogen and depressurization with a vacuum pump, the methyl ethyl ketone is heated to the reflux temperature, and this is stirred and refluxed. However, a monomer solution consisting of 20 parts (0.05 mol part) of ALE-200 {Nichiyu Co., Ltd., acrylic acid ester of dodecyl alcohol-4 mol adduct} and 20 parts of methyl ethyl ketone, and dimethyl-2,2 '-A catalyst solution consisting of 0.4 part of azobis (2-methylpropinate) and 19.6 parts of methyl ethyl ketone was started to be added dropwise at the same time, the monomer solution was added dropwise in 3 hours, and the catalyst solution was added dropwise in 2 hours. I finished it. After the completion of these droppings, the mixture was aged for 3 hours while stirring and refluxing. Then, methyl ethyl ketone was distilled off under reduced pressure to obtain a polymer (a1: polymer of acrylic acid ester of dodecyl alcohol-ethylene oxide 4 mol adduct). The weight average molecular weight (Mw) of the polymer (a1) was 20,000.

<Manufacturing example 2>
A polymer (a2: polymer of acrylic acid ester of dodecyl alcohol-ethylene oxide 4 mol adduct) was obtained in the same manner as in <Production Example 1> except that "methyl ethyl ketone" was changed to "isopropyl alcohol". The weight average molecular weight (Mw) of the polymer (a2) was 0.41 million.

<Manufacturing example 3>
"ALE-200 {Nichiyu Co., Ltd., Dodecyl alcohol-acrylic acid ester of 4 mol of ethylene oxide} 20 parts (0.05 mol part)" was added to "ALE-200 15 parts (0.038 mol part) and PSE- 1300 {Nichiyu Co., Ltd., Octadecyl alcohol-methacrylic acid ester of 30 mol of ethylene oxide} changed to 5 parts (0.003 mol part), "dimethyl-2,2'-azobis (2-methylpro) Pinate) 0.4 parts and isopropyl alcohol 19.6 parts "was changed to"dimethyl-2,2'-azobis (2-methylpropinate) 0.05 parts and methyl ethyl ketone 19.95 parts ", but < A polymer (a3: a copolymer of acrylic acid ester of dodecyl alcohol-ethylene oxide 4 mol adduct / metaacry acid ester of octadecyl alcohol-ethylene oxide 30 mol adduct) was obtained in the same manner as in Production Example 1>. The weight average molecular weight (Mw) of the polymer (a3) was 40,000.

<Manufacturing example 4>
158 parts (1 mol part) of Calcol 1098 {Kao Co., Ltd., decyl alcohol} and potassium hydroxide 5 in a pressure resistant reaction vessel capable of stirring, heating, cooling, dropping, nitrogen substitution, pressurization with nitrogen and depressurization with a vacuum pump. After charging the parts, dehydration was performed at 120 ° C. under a reduced pressure of 0.6 to 1.3 kPa for 2 hours. Then, 220 parts (5 mol parts) of ethylene oxide (EO) was added dropwise at 120 ° C. under reduced pressure over 12 hours, and stirring was further continued at 120 ° C. for 2 hours to react the remaining (EO). Next, the reaction catalyst was removed by a method using an alkaline adsorbent {synthetic aluminosilicate; Kyoward (registered trademark) 600, Kyowa Chemical Industry Co., Ltd.} (Japanese Patent Laid-Open No. 53-123499, etc.) {hereinafter, "catalyst removal". Abbreviated as "processing". } To obtain a decyl alcohol-ethylene oxide 5 mol adduct.

In a reaction vessel equipped with a Dean Stark extractor with a cooler, 378 parts (1 mol) of the decyl alcohol-ethylene oxide 5 mol adduct, 76 parts (1.06 mol) of acrylic acid, and paratoluenesulfonic acid produced above were placed. After charging 1.2 parts, 0.5 part of hydroquinone and 400 parts of toluene, the temperature was raised, and water was removed from the reaction system by azeotropic boiling while refluxing toluene. After continuing the reaction for 5 hours under the same conditions, the mixture was cooled to 25 ° C. and washed twice with 5% aqueous sodium hydroxide solution and three times with ion-exchanged water. Finally, toluene was removed by vacuum distillation to obtain an acrylic acid ester of a decyl alcohol-ethylene oxide 5 mol adduct.

20 parts (0.05 mol part) of "ALE-200 {Nichiyu Co., Ltd., acrylic acid ester of dodecyl alcohol-ethylene oxide 4 mol adduct}" was produced above, and "decyl alcohol-polyethylene oxide 5 mol adduct acrylic" was produced. Acrylic acid ester polymer of polymer (a4: decyl alcohol-polyethylene oxide 5 mol adduct) in the same manner as in <Production Example 1> except that it was changed to "acid ester} 20 parts (0.046 mol part)". ) Was obtained. The weight average molecular weight (Mw) of the polymer (a4) was 21,000.

<Manufacturing example 5>
"ALE-200 {Nichiyu Co., Ltd., Dodecyl Alcohol-Ethylene Oxide 4 mol Acrylic Ester} 20 parts (0.05 mol part)" was changed to "ALE-200 {Nichiyu Co., Ltd., Dodecyl Alcohol-Ethylene Oxide 4 mol Additive acrylic acid ester} 20 parts (0.05 mol part) and light acrylate 9EG-A {Kyoeisha Chemical Co., Ltd. (“light acrylate” is a registered trademark of the company), polyethylene glycol diacrylate} 0.8 Changed to "parts (0.0015 mol parts)", "dimethyl-2,2'-azobis (2-methylpropinate) 0.4 parts and methyl ethyl ketone 19.6 parts" to "dimethyl-2,2'- Acrylic of polymer (a5: dodecyl alcohol-ethylene oxide 4 mol adduct) in the same manner as in <Production Example 1> except that it was changed to 0.8 part of azobis (2-methylpropinate) and 19.2 parts of methyl ethyl ketone. (Polymer of acid ester / polyethylene glycol diacrylate) was obtained. The weight average molecular weight (Mw) of the polymer (a5) was 18,000.

<Manufacturing example 6>
270 parts (1 mol part) of Calcol 8098 {Kao Co., Ltd., octadecyl alcohol} and potassium hydroxide 5 in a pressure resistant reaction vessel capable of stirring, heating, cooling, dropping, nitrogen substitution, pressurization with nitrogen and depressurization with a vacuum pump. After charging the parts, dehydration was performed at 120 ° C. under a reduced pressure of 0.6 to 1.3 kPa for 2 hours. Then, 1160 parts (20 mol parts) of propylene oxide (PO) was added dropwise at 120 ° C. under reduced pressure over 12 hours, and stirring was further continued at 120 ° C. for 2 hours to react the remaining (PO). Then, it is "catalyst-removed" using an alkaline adsorbent to perform a nonionic activator (b11: octadecyl alcohol-propylene oxide 20 mol adduct {R ² : octadecyl, OA: oxypropylene, m: 20, p = 0, q = 1}) was obtained.

<Manufacturing example 7>
In a pressure-resistant reaction vessel, 715 parts (0.5 mol part) of nonionic activator (b11), Lunac S-98 {Kao Corporation, stearic acid (98% or more), and "Lunac" are registered trademarks of the same company. } 142 parts (0.5 mol part) and 4 parts of methanesulfonic acid {reagent special grade, Wako Pure Chemical Industries, Ltd.} are charged, pressurized with nitrogen gas to 0.3 MPa, and then 0.12 MPa. After repeating the operation of discharging up to 150 times (hereinafter, this operation using nitrogen gas is abbreviated as "nitrogen substitution"), the temperature was raised to 150 ° C. Then, the pressure was gradually reduced by a vacuum pump, and the mixture was reacted at 0.6 to 1.3 kPa at 150 ° C. for 12 hours to obtain a stearic acid ester of a nonionic activator (b12: octadecyl alcohol-propylene oxide 20 mol adduct {R ² : octadecyl, OA: oxypropylene, m: 20, R ³ : octadecanoyl, p = 1, q = 0}) was obtained.

<Manufacturing example 8>
158 parts (1 mol part) of Calcol 1098 {Kao Co., Ltd., decyl alcohol} and potassium hydroxide 5 in a pressure resistant reaction vessel capable of stirring, heating, cooling, dropping, nitrogen substitution, pressurization with nitrogen and depressurization with a vacuum pump. After charging the parts, the mixture was dehydrated at 120 ° C. under a reduced pressure of 0.6 to 1.3 kPa for 2 hours. Then, 880 parts (20 mol parts) of ethylene oxide (EO) was added dropwise at 120 ° C. under reduced pressure over 12 hours, and stirring was continued at 120 ° C. for 2 hours to react the remaining (EO), and further propylene oxide. 1160 parts (20 mol parts) of (PO) was added dropwise over 12 hours, and stirring was further continued at 120 ° C. for 2 hours to react the remaining (PO). Then, it is "catalyst-removed" using an alkaline adsorbent to perform a nonionic activator (b13: decyl alcohol-ethylene oxide 20 mol-propylene oxide 20 mol adduct {R ² : decyl, OA: oxyethylene / oxypropylene (block). Addition), m: 20/20, p = 0, q = 1}).

<Manufacturing example 9>
"Ethylene oxide (EO) 880 parts (20 mol parts)", "Propylene oxide (PO) 1160 parts (20 mol parts)""Ethylene oxide (EO) 616 parts (14 mol parts)", "Propylene oxide (PO) 1508" In the same manner as in <Production Example 8>, the nonionic activator (b14: decyl alcohol-ethylene oxide 14 mol-propylene oxide 26 mol adduct {R ² : decyl, OA: Oxyethylene / oxypropylene (block-shaped), m: 14/26, p = 0, q = 1}) was obtained.

<Manufacturing example 10>
"Nonion activator (b11) 715 parts (0.5 mol part)" was added to "New Pole LB-1715 (b15: butyl alcohol-propylene oxide 40 mol adduct {R ² : butyl, OA: oxypropylene, m: 40". , P = 0, q = 1}, Sanyo Kasei Kogyo Co., Ltd., "New Pole" is a registered trademark of the company.) <Manufacturing example 7> except that it was changed to 1197 parts (0.5 mol parts). In the same manner as above, the nonionic activator (b16: butyl alcohol-stearic acid ester of 40 mol adduct of propylene oxide {R ² : butyl, OA: oxypropylene, m: 40, R ³ : octadecanoyl, p = 1, q = 0}) was obtained.

<Manufacturing example 11>
In a reaction vessel capable of heating, stirring, cooling, dropping, pressurizing and depressurizing, sucrose {trade name; sucrose, Wako Pure Chemical Industries, Ltd., first grade} 342 parts (1 mol part) and dimethylformamide (DMF) {Mitsubishi Gas Chemicals Co., Ltd.} Add 1000 parts, replace with nitrogen and mix uniformly, then raise the temperature to 100 ° C. with stirring, and add 1856 parts (32 mol parts) of propylene oxide (PO) at the same temperature for 4 hours. After dropping over, stirring was continued for 30 minutes at the same temperature to react the remaining PO, and then 576 parts (8 mol parts) of butylene oxide (BO) was added dropwise at the same temperature over 2 hours, and then 4 Stirring for hours was continued to react the remaining BO. rice field. Then, the mixture was heated to 120 ° C., the DMF was distilled off under a reduced pressure of 0.01 to 0.1 MPa while maintaining the same temperature, and then cooled to cool the nonionic activator (b17: sucrose-propylene oxide 32 mol-butylene oxide). An 8-molar adduct {R ² : reaction residue of sucrose, OA: oxypropylene / oxybutylene (block-like), m: 32/8, p = 0, q = 8}) was obtained.

<Manufacturing example 12>
Similar to Production Example 1 of Patent Document 1, hydrocarbon oil (d1) [Pure Spin E, Cosmo Petroleum Lubricants Co., Ltd.] 99.9 parts and hydrophobic silica [Nippil SS-10, volume average particle size] are placed in a stainless beaker. 3 μm, Toso Silica Co., Ltd.] After adding 0.1 part, raise the temperature to 180 ° C while stirring with a homogenizer (Highflex Disperser HG-92G, Titec Co., Ltd.) at 4000 rpm, and at this temperature. Further, the mixture was heated and stirred for 3 hours to obtain a hydrophobic silica dispersion (e1). In the dispersion test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)], it was confirmed that there were no grains of 5 microns or more.

<Examples 1 to 9, comparative example>
The compositions and amounts (parts) shown in Table 1 are uniformly mixed at 40 ° C. to prepare the defoaming agents (1) to (9) of Examples 1 to 9 and the defoaming agent (H1) of Comparative Example. did.

(B18): Aoki Oil & Fat Industry Co., Ltd., Finesurf TDP-04K (Tridecyl alcohol propylene oxide 4 mol adduct {R ² : Tridecyl, OA: oxypropylene, m: 4, p = 0, q = 1})
(B19): Sanyo Chemical Industries, Ltd., Ionet S-85 (“Ionet” is a registered trademark of the company. Sorbitan trioleic acid ester {R ² : Reaction residue of sorbitan, m: 0, R ³ : 9 -Octadecenoyl, p = 3, q = 1})
(B20): Kao Corporation, Leodor 430V (polyoxyethylene (degree of polymerization: 30) sorbitol tetraoleic acid ester {R ² : reaction residue of sorbitol, oxyethylene, m: 30, R ³ : 9-octadecenoyl, p. = 4, q = 2})

(C1): Shin-Etsu Chemical Co., Ltd., Polyester Modified Silicone, X-22-4515 (HLB = 5)
(C2): Toray Dow Corning Co., Ltd., Polyether Modified Silicone, FZ-2203 (HLB = 2)

<Creation of base paint for evaluation>
A paint was obtained by grinding and let-down using an Excel autohomogenizer (Nippon Seiki Co., Ltd., Model ED) equipped with an impeller type blade with the following raw material composition. This paint was diluted with water to 80 KU (25 ° C.) with a Stormer viscometer (JIS K5600-2-2: 1999 “5. Stormer viscometer method”) to obtain a glossy base paint.

* 1: Dispersant (San Nopco Ltd.)
* 2: Thickener (San Nopco Ltd.)
* 3: Titanium dioxide (Ishihara Sangyo Co., Ltd., "Typake" is a registered trademark of the company.)
* 4: Binder resin (Dow Chemical Company, "Primal" is a registered trademark of Rome and Haas Company)
* 5: Film-forming conditioner (Eastman Chemical Company, "Texanol" is a registered trademark of Yoshimura Chemical Co., Ltd.

<Adjustment of evaluation paint>
Add 0.2 parts each of the defoaming agents (1) to (9) of the present invention or the defoaming agent (H1) for comparison to 100 parts of the glossy base paint to make an Excel autohomogenizer equipped with a chorus type blade. The mixture was stirred and mixed at 25 ° C., 1500 rpm for 2 minutes to obtain a coating material for evaluation.
Further, an evaluation paint (blank) was obtained in the same manner as above except that no defoaming agent was added.

<Evaluation of defoaming property>
Using a medium wool roller (Otsuka Brush Manufacturing Co., Ltd.), apply the evaluation paint on a 15 cm x 15 cm tin plate, and immediately after painting, the number of bubbles generated in 3 cm square and the time until the bubbles disappear ( Disappearance time; seconds) was visually determined. The smaller the number of bubbles immediately after coating and the shorter the time until the bubbles disappear, the better the defoaming property.

<Evaluation of gloss>
After degreasing the glass plate {thickness 5 mm, 15 x 15 cm} with acetone / cloth, apply the evaluation paint with an applicator so that the wet film thickness is 100 μm under the conditions of 25 ° C and 60% relative humidity { After 10 × 10 cm}, it was allowed to stand for 24 hours to prepare an evaluation coating film. The 60 ° gloss on the surface of the coating film was measured at three points by a gloss meter (DM26D, Murakami Color Technology Laboratory Co., Ltd.) based on ISO 2813: 1994, and the average value was calculated. The larger the value, the better the glossiness.

The defoaming agent of the present invention had the same or better defoaming property and was excellent in glossiness as compared with the defoaming agent for comparison.

Although the defoaming agent of the present invention can be used for all purposes, it is effective against an aqueous foaming liquid, and is, for example, in the paper pulp manufacturing industry (pulping process, paper making process, coating process, etc.), construction industry ( It can be applied to bubbles generated in various processes such as manufacturing process), dye industry, dyeing industry, fermentation industry, synthetic resin manufacturing industry, synthetic rubber manufacturing industry, ink, paint industry and textile processing industry. Of these, it is suitable as a defoaming agent for paints, and further suitable as a defoaming agent for water-based paints, and water-based paints (water-based building exterior paints, building interior paints, water-based inks, paper coating paints, etc.) Of these, it is most suitable as a defoaming agent for glossy paints.

Claims (4)

A polymer (A) having a (meth) acrylate represented by the formula (1) or a (meth) acrylate represented by the formula (1) and (meth) acrylic acid, a (meth) acrylic acid alkyl ester, The constituent unit is another monomer selected from styrene, acrylonitrile and maleic acid, and the content of the other monomer unit is 1 to 1 based on the weight of the (meth) acrylate unit represented by the formula (1). The copolymer (A) and the nonionic activator (B) are contained in an amount of 9% by weight, and the nonionic activator (B) is a compound represented by the formula (2) and (co). A defoaming agent characterized in that the weight ratio (A: B) of the polymer (A) to the nonionic activator (B) is 1:99 to 40:60 .
M- (OA) _n R ¹ (1)

M is a (meth) acryloyloxy group, OA is an oxyalkylene group having 2 to 4 carbon atoms {(OA) _n may be composed of a plurality of types of OA}, n is an integer of 1 to 40, and R ¹ is carbon. It is any one hydrocarbon group selected from an alkyl group having 7 to 24 carbon atoms, an alkenyl group having 7 to 23 carbon atoms, or an aryl group having 7 to 15 carbon atoms.

R ² is a reaction residue of a monool having 1 to 30 carbon atoms or a saccharide having 4 to 8 valences, R ³ is an organic group having 1 to 25 carbon atoms, and OA is an oxyalkylene group having 2 to 4 carbon atoms {(OA). _m may be composed of a plurality of types of OA}, m is an integer of 0 to 100, and when a plurality of m exists in one molecule, they may be the same or different, and p is 0, 1, or 4. An integer of -8, q is an integer of 0, 1 or 4-8, and the sum of p and q is 1 or 4-8. However, when at least one m is 0, p is an integer of 1 or 4 to 8, and q is an integer of 0 or 3 to 7. (Co) The defoaming agent according to claim 1, wherein the weight ratio (A: B) of the polymer (A) to the nonionic activator (B) is 3: 97 to 25:75. Claim 1 further contains silicone (C), and the content of silicone (C) is 1 to 100 parts by weight with respect to a total of 100 parts by weight of the (co) polymer (A) and the nonionic activator (B). Or the defoaming agent according to 2. A water-based coating composition comprising the water-based coating material and the defoaming agent according to any one of claims 1 to 3.