JP7216426B2 - Defoamer - Google Patents

Description

The present invention relates to antifoam agents.

A defoaming agent comprising an amide (A) and a hydrocarbon oil (B), wherein the content of the aroma component in (B) is 1 to 6% by weight based on the weight of (B), (B ) contains 25 to 35% by weight of the naphthenic component and (B) contains 59 to 74% by weight of the paraffinic component (Patent Document 1).

JP 2005-270890 A

Although the antifoaming agent described in Patent Document 1 exhibits excellent antifoaming properties, there is a problem that repelling may occur when applied to paint to form a thin coating film.
An object of the present invention is to provide an antifoaming agent which is excellent in antifoaming properties and does not cause repelling even when applied to paints to form thin coating films.

The antifoaming agent of the present invention is characterized by consisting only of oxidized polyethylene wax (A) and hydrocarbon oil (B) having a kinematic viscosity (40° C.) of 20 to 40 mm ² /s , or
It consists only of oxidized polyethylene wax (A), hydrocarbon oil (B) having a kinematic viscosity (40° C.) of 20 to 40 mm ² /s, and polyoxyalkylene compound (C) represented by general formula (1). This is the gist.
R ¹ O(EO)n(PO)m(EO)n-R ¹ (1)

R ¹ is an acyl group having 10 to 22 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, O is an oxygen atom, n is an integer of 1 to 5, m is an integer of 10 to 50, (EO)n and (PO)m represents a block-like bond.

The feature of the emulsion paint of the present invention is summarized in that it contains the antifoaming agent, water and binder described above.

The gist of the feature of the pressure-sensitive adhesive of the present invention is that it contains the antifoaming agent, water and binder described above.

The antifoaming agent of the present invention exhibits excellent antifoaming properties and does not cause repelling even when applied to a paint to form a thin coating film.

Since the emulsion paint of the present invention contains the antifoaming agent, even when a thin coating film is formed, the emulsion paint has excellent antifoaming properties and does not cause repelling.

Since the pressure-sensitive adhesive of the present invention contains the antifoaming agent, even if a thin coating film is formed, the adhesive has excellent antifoaming properties and does not cause repelling.

The oxidized polyethylene wax (A) includes low density oxidized polyethylene wax, high density oxidized polyethylene wax, acid modified polyethylene wax and low density decomposed polyethylene wax.

The acid value (mgKOH/g) of the oxidized polyethylene wax is preferably 6-20, more preferably 8-18, particularly preferably 9-17. When it is in this range, even if it is applied to a paint to form a thin coating film, the antifoaming property is further excellent, and cissing does not occur.

The acid value is JIS K5902-1969 "5.4 acid value" (approximately 2 g of sample is accurately weighed in a 300 ml Erlenmeyer flask, dissolved in 50 ml of ethyl alcohol / benzene mixture (volume ratio 1: 2), phenolphthalein is titrated with N/2 ethyl alcoholic potassium hydroxide solution as an indicator, and the end point of neutralization is when the slightly reddish color does not disappear for 30 seconds, and the acid value is calculated.).

The oxidized polyethylene wax (A) is readily available from the market, and includes Sanwax E-310 (Sanyo Chemical Industries, Ltd., acid value 15 mgKOH/g, "Sanwax" is a registered trademark of the same company), Sanwax E -330 (Sanyo Chemical Industries Co., Ltd., acid value 17 mgKOH / g), Sanwax E-250P (Sanyo Chemical Industries Co., Ltd., acid value 20 mgKOH / g), Hiwax 4051E (Mitsui Chemicals Co., Ltd., acid value 12 mgKOH / g) , Hi-Wax 4052E (Mitsui Chemicals, Inc., acid value 20 mgKOH / g), Hi-Wax 4053E (Mitsui Chemicals, Inc., acid value 17 mgKOH / g), Hi-Wax 4252E (Mitsui Chemicals, Inc., acid value 17 mgKOH / g), Epolen E-10 (Westlake Longview Corporation, acid value 17 mgKOH/g, "Epolen" is a registered trademark of Westlake Longview Corporation.), Epolen E-14 (Westlake Longview Corporation, acid value 17 mgKOH/g) , Epolen E-16 (Westlake Longview Corporation, acid value 17 mgKOH/g), Epolen E-20 (Westlake Longview Corporation, acid value 17mgKOH/g), Epolen EE-2 (Westlake Longview Corporation, acid value 16 mgKOH / g), LicowaxPED521 (Clariant Chemicals, acid value 15 mgKOH / g, "LICOWAX" is a registered trademark of Clariant AG.), LicowaxPED121 (Clariant Chemicals, acid value 16 mgKOH / g), LicowaxPED191 (Clariant Chemicals, acid value 15 mg KOH / g), Licowax PED 192 (Clariant Chemicals, acid value 20 mg KOH / g), VESTOWAX C20 (Evonik, acid value 8 mg KOH / g, "VESTOWAX" is a registered trademark of Evonik Degussa GmbH) and VESTOWAX J324 ( Evonik, acid value 10 mgKOH/g) and the like.

Hydrocarbon oils (B) include lubricating oils, spindle oils, paraffin oils {liquid paraffin (n-paraffin, isoparaffin, etc.), ozokerite, squalene, pristane, paraffin, ceresin, squalene, vaseline, etc.} and mixtures thereof. Available.

The kinematic viscosity (40° C., mm ² /s) of the hydrocarbon oil (B) is preferably 20-40, more preferably 22-38, particularly preferably 26-34. When it is in this range, even if it is applied to a paint to form a thin coating film, the antifoaming property is further excellent, and cissing does not occur.

Hydrocarbon oil (B) is easily available from the market, Cosmo Pure Spin G (Cosmo Oil Co., Ltd., kinematic viscosity (40 ° C.) 21 mm ² / s, “Cosmo” and “Pure Spin” are Cosmo Energy Holdings Co., Ltd. ), Cosmo SC22 (Cosmo Oil Co., Ltd., kinematic viscosity (40 ° C.) 22 mm ² / s), Cosmo Neutral 100 (Cosmo Oil Co., Ltd., kinematic viscosity (40 ° C.) 21 mm ² / s) and Cosmo Neutral 150 (Cosmo Oil Co., Ltd., kinematic viscosity (40° C.) 33 mm ² /s) and the like. Hydrocarbon oils other than the products exemplified here can be used as long as they are within the above range of kinematic viscosity, and a mixture of multiple types of hydrocarbon oils may be used. A mixture of hydrogen oil may also be used. When mixing a plurality of types of hydrocarbon oils, it is preferable that the difference in kinematic viscosity is within 15 mm ² /s.

The content (% by weight) of the oxidized polyethylene wax is preferably 1-10, more preferably 3-7, based on the total weight of the oxidized polyethylene wax (A) and the hydrocarbon oil (B). When it is in this range, even if it is applied to a paint to form a thin coating film, the antifoaming property is further excellent and repelling does not occur.

The content (% by weight) of the hydrocarbon oil (B) is preferably 90-99, more preferably 93-97, based on the total weight of the oxidized polyethylene wax (A) and the hydrocarbon oil (B). When it is in this range, even if it is applied to a paint to form a thin coating film, the antifoaming property is further excellent, and cissing does not occur.

The antifoaming agent of the present invention preferably further contains a polyoxyalkylene compound (C) represented by general formula (1). When the polyoxyalkylene compound (C) is contained, even if it is applied to a coating material to form a thin coating film, the antifoaming property is further excellent and repelling does not occur.

R ¹ O(EO)n(PO)m(EO)n-R ¹ (1)

R ¹ is an acyl group having 10 to 22 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, O is an oxygen atom, n is an integer of 1 to 5, m is an integer of 10 to 50, (EO)n and (PO)m represents a block-like bond.

The polyoxyalkylene compound (C) of general formula (1) can be easily obtained by esterification of a polyoxyethylene-polyoxypropylene block adduct and a carboxylic acid.

Polyoxyethylene-polyoxypropylene block adducts are readily available on the market, and include Newpol PE-61 (Sanyo Chemical Industries, Ltd., "Newpol" is a registered trademark of the company), Newpol PE-62 ( Sanyo Chemical Industries Co., Ltd.), Brownon P-171 (Aoki Oil Industry Co., Ltd.), and the like.

Carboxylic acids include carboxylic acids having 10 to 22 carbon atoms, such as decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, octadecenoic acid, octadecadienoic acid and isooctadecanoic acid. is mentioned.

When the polyoxyalkylene compound (C) represented by the general formula (1) is included, the content (% by weight) of the polyoxyalkylene compound (C) is the content of the oxidized polyethylene wax (A) and the hydrocarbon oil (B). Preferably 0.1 to 10, more preferably 0.5 to 5, based on total weight.

The antifoaming agent of the present invention can be produced by a known method, for example, a production method including the following steps (1) and (2) can be applied.
First, the oxidized polyethylene wax (A) and the hydrocarbon oil (B) are heated with stirring to a temperature higher than the melting point of the oxidized polyethylene wax (A) to uniformly dissolve the oxidized polyethylene wax (A) and the hydrocarbon oil (B). obtaining a mixed solution (1);
Step (2) of obtaining an antifoaming agent by cooling the mixture to 40° C. or less while stirring.

A portion of hydrocarbon oil (B) may be used in step (1) and the remainder of hydrocarbon oil (B) may be used in step (2). That is, the liquid mixture may be added to the remainder of the hydrocarbon oil (B) and cooled, or the remainder of the hydrocarbon oil (B) may be added to the liquid mixture and cooled.

When the polyoxyalkylene compound (C) is used, it may be added at any step and at any timing as long as uniform mixing is possible.

After the step (2), a miniaturization treatment may be performed. A ball mill, disper mill, homogenizer, Gaulin homogenizer, or the like can be used for the refining treatment. The size of particles of the oxidized polyethylene wax (A) precipitated by cooling can be adjusted by the refinement treatment.

The heating temperature (°C) in step (1) is appropriately determined depending on the type of oxidized polyethylene wax used, etc., but is preferably 60 to 160, more preferably 80 to 140, and particularly preferably 100 to 120.

The defoamer of the present invention is effective against aqueous foaming liquids. Therefore, it can be used as an antifoaming agent for paints and an antifoaming agent for various production processes (paper making process, fermentation process, waste water treatment process, monomer stripping process, polymer polymerization process, etc.). Among these, it is suitable as a defoaming agent for water-based paints, and further water-based paints (emulsion paints (water-based architectural exterior paints, architectural interior paints, etc.), water-based inks, paper coating paints, adhesives (for non-woven fabrics) Adhesives, adhesives for metal foils, adhesives for films, etc.), etc.), it is most suitable for emulsion paints and adhesives.

The emulsion paint may contain water and a binder, and examples of the binder include vinyl acetate resins, acrylic resins, styrene resins, halogenated olefin resins, urethane resins, silicone resins, fluorine atom-containing silicone resins, and the like. , is effective against both.

The adhesive may contain water and a binder, and examples of the binder include vinyl acetate resins, acrylic resins, styrene resins, halogenated olefin resins, urethane resins, silicone resins, fluorine atom-containing silicone resins, and the like. , is effective against both.

The content (% by weight) of the antifoaming agent of the present invention is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, based on the weight of the water-based paint when applied to the water-based paint. is. Moreover, when applying it to various manufacturing processes, it can determine suitably according to the operating condition of each process.

Hereinafter, unless otherwise specified, parts means parts by weight and % means % by weight.
<Example 1>
30 parts of VESTOWAX C20 {acid value 8 mgKOH/g, Evonik} and 100 parts of Cosmo Neutral SC22 {kinematic viscosity 22 mm ² /s, Cosmo Oil Lubricants Co., Ltd.} were heated to 120° C. with stirring, and further heated at this temperature. After continuing heating and stirring for 15 minutes to obtain a mixed liquid, the mixed liquid was added to 870 parts of Cosmo Neutral SC22 adjusted to 20°C while stirring and cooling, and stirred at 40°C or lower for 15 minutes. After that, an Excel auto homogenizer equipped with impeller-type blades was used for 15 minutes at 4,000 rpm to obtain a defoaming agent (S1) of the present invention.

<Example 2>
"VESTOWAX C20 {acid value 8 mgKOH/g, Evonik}" was changed to "Sunwax E-330 {acid value 17 mgKOH/g, Sanyo Chemical Industries Co., Ltd.}", "Cosmo Neutral SC22 {kinematic viscosity 22mm ² / s Cosmo Oil Lubricants Co., Ltd.}” was changed to “Cosmo Neutral 150 {kinematic viscosity 33 mm ² /s Cosmo Oil Lubricants Co., Ltd.}”, the antifoaming agent (S2) of the present invention was added in the same manner as in Example 1. Obtained.

<Example 3>
EPOLENE E10 {acid value 17 mgKOH/g, Westlake Longview Corporation} 70 parts, Cosmo Neutral 150 {kinematic viscosity 22 mm ² /s, Cosmo Oil Lubricants Co., Ltd.} 130 parts were heated to 100 ° C. while stirring. After continuing heating and stirring for an additional 15 minutes to obtain a mixed liquid, the mixed liquid was added to 800 parts of Cosmo Neutral 150 adjusted to 20°C while stirring and cooling, and stirred at 40°C or lower for 15 minutes. Then, 50 parts of octadecenoic acid diester from Nieupol PE62 (Sanyo Chemical Industries, Ltd.) was added, and the antifoaming agent of the present invention was finely treated by stirring at 4000 rpm for 15 minutes in an Excel auto homogenizer equipped with impeller blades. (S3) was obtained.

<Example 4>
Same as Example 3 except that "50 parts of octadecenoic acid diester of Newpol PE62 {Sanyo Chemical Industries Co., Ltd.}" was changed to "5 parts of tetradecanoic acid diester of Braunon P-171 {Aoki Oil Industry Co., Ltd.}". to obtain the antifoaming agent (S4) of the present invention.

<Example 5>
Same as Example 3 except that "50 parts of octadecenoic acid diester of Newpol PE62 {Sanyo Chemical Industries Co., Ltd.}" was changed to "5 parts of octadecanoic acid diester of Newpol PE61 {Sanyo Chemical Industries Co., Ltd.}". to obtain the antifoaming agent (S5) of the present invention.

<Comparative Example 1>
An antifoaming agent (H1) for comparison was obtained based on the description of Example 1 of Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-270890).

That is, Kaowax EB-P {ethylene bisstearylamide, Kao Corporation} 40 parts, Cosmo Neutral SC22 {Cosmo Oil Lubricants Co., Ltd.} 200 parts, Newpol LB-625 {Sanyo Chemical Industries Co., Ltd.} 60 parts and Nipsil SS -10 {Nippon Silica Co., Ltd.} 30 parts is put into a reaction vessel that can be heated, stirred and cooled, and then heated to 130 ° C. with stirring, and the heating and stirring is continued for another 15 minutes at this temperature for carbonization. A hydrogen oil solution was obtained. Next, the hydrocarbon oil solution was added to 670 parts of Cosmo Neutral SC22 adjusted to 5°C while stirring and cooling (liquid temperature: 38°C), and after stirring for 15 minutes, an Excel auto homogenizer equipped with an impeller-type blade was added. A dispersion liquid was obtained by stirring at 4000 rpm for 15 minutes, and it was confirmed by a dispersion degree test {JIS K5600-2-5:1999 (corresponding to ISO 1524:1983)} that there were no grains of 5 microns or more.
This dispersion was heated to 80° C. and stirred at the same temperature for 2 hours to obtain an antifoaming agent (H1) for comparison.

Using the antifoaming agents S1 to S5 and H1 obtained in Examples 1 to 5 and Comparative Example 1, emulsion paints and adhesives were prepared as follows, and antifoaming properties and repelling were evaluated by the following methods. .

(1) Preparation of emulsion base paint The raw material composition below was ground and let down using an Excel Auto Homogenizer (manufactured by Nippon Seiki Co., Ltd., Model ED) equipped with impeller blades to form an emulsion.
Then, this emulsion was diluted with water to 77 KU (25° C.) with a Stomer viscometer (JIS K5400-1990) to obtain an emulsion base paint.

*1 Dispersant, San Nopco Co., Ltd. *2 Thickener, San Nopco Co., Ltd. *3 Titanium oxide, Ishihara Sangyo Co., Ltd. "Tipake" is a registered trademark of the company.
*4 Acrylic emulsion, DIC Corporation, and “Boncoat” are registered trademarks of DIC Corporation.
*5 Preservative, San Nopco Co., Ltd. *6 Film-forming modifier, Eastman Chemical Company, "Texanol" is a registered trademark of Yoshimura Yukagaku Co., Ltd.

(2) Preparation of emulsion paint Add 3 parts of any of defoaming agents S1 to S5 and H1 to 100 parts of the emulsion base paint, and use an Excel auto homogenizer equipped with impeller blades at 15 to 25 ° C., 2000 rpm, 5 After stirring and mixing for a minute, emulsion paints 1 to 6 for evaluation were obtained.

(3) Preparation of adhesive 100 parts of an acrylic adhesive base (containing no antifoaming agent. Moisture content 50%) provided by an adhesive film maker, 0.1 part of any of antifoaming agents S1 to S5 and H1 In addition, they were stirred and mixed at 15 to 25° C. and 500 rpm for 30 minutes using an Excel auto homogenizer equipped with impeller-type blades to obtain adhesives 1 to 6 for evaluation.

(4) Evaluation of defoaming property and repellency (4-1) Defoaming property of emulsion paint Wet the emulsion paint for evaluation on a PET film (20 cm × 20 cm) using a medium wool roller (Otsuka Brush Manufacturing Co., Ltd.) Roller coating was applied to a film thickness of 150 µm, and the amount of residual bubbles after 30 seconds was visually counted and shown in the table below. The smaller the amount of residual foam, the better the antifoaming property.

(4-2) Defoaming property of the adhesive 500 mL of the adhesive for evaluation is put in a standard automixer DL-7524 (Kai Corporation), stirred for 5 minutes at a stirring speed scale of 12, and then transferred to a 1 L glass graduated cylinder. The foam height immediately after transfer was read and recorded in the table below. A lower foam height means better defoaming.

(4-3) Repelling of emulsion paint After degreasing the PET film {20 × 20 cm} with acetone / cloth, the emulsion paint for evaluation was applied to a wet film thickness of 25 μm under the conditions of 25 ° C. and 60% relative humidity. was applied with an applicator (Baker film applicator), the surface of the coating film was observed, and the number of cissing marks was visually counted, and the results are shown in the table below. In addition, the smaller the numerical value, the smaller the cissing, which is preferable.

(4-4) Repelling of adhesive After degreasing the OPP film {20 × 20 cm} with acetone / cloth, apply the adhesive for evaluation so that the wet film thickness is 50 μm under the conditions of 25 ° C. and 60% relative humidity. After coating with a bar coater (spiral bar coater), the coating film surface was observed, and the number of cissing marks was visually counted, and the results are shown in the table below. In addition, the smaller the numerical value, the smaller the cissing, which is preferable.

Emulsion paints and pressure-sensitive adhesives using the antifoaming agent of the present invention exhibit equivalent or better antifoaming properties than those using the comparative antifoaming agent even when applied to the paint to form a thin coating film. and repellency was remarkably small.

Claims (6)

consisting only of oxidized polyethylene wax (A) and hydrocarbon oil (B) having a kinematic viscosity (40° C.) of 20 to 40 mm ² /s , or
It consists only of oxidized polyethylene wax (A), hydrocarbon oil (B) having a kinematic viscosity (40° C.) of 20 to 40 mm ² /s, and polyoxyalkylene compound (C) represented by general formula (1). A defoamer characterized by :
R ¹ O(EO)n(PO)m(EO)n-R ¹ (1)

R ¹ is an acyl group having 10 to 22 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, O is an oxygen atom, n is an integer of 1 to 5, m is an integer of 10 to 50, (EO)n and (PO)m represents a block-like bond. Based on the total weight of the oxidized polyethylene wax (A) and the hydrocarbon oil (B), the content of the oxidized polyethylene wax (A) is 1 to 10% by weight and the content of the hydrocarbon oil (B) is 90 to 99% by weight. %. 3. The antifoaming agent according to claim 1, wherein the oxidized polyethylene wax (A) has an acid value of 6 to 20 mgKOH/g. The content of the polyoxyalkylene compound (C) is 0.1 to 10% by weight based on the total weight of the oxidized polyethylene wax (A) and the hydrocarbon oil (B), according to any one of claims 1 to 3. defoamer. An emulsion paint comprising the antifoaming agent according to any one of claims 1 to 4 , water and a binder. A pressure sensitive adhesive comprising the antifoaming agent according to any one of claims 1 to 4 , water and a binder.