JPWO2013121851A1 - Release agent emulsion composition for die casting - Google Patents

Abstract

The present invention includes (A) an alkyl group having 6 or more carbon atoms and an aralkyl group-containing organopolysiloxane, (B) a polyether group-containing organopolysiloxane, and (C) a mold release for die casting, Agent emulsion composition. According to the present invention, it is possible to provide a release agent emulsion composition for die casting that is excellent in adhesion to a mold particularly at a high temperature and has good releasability.

Description

  This application claims priority based on Japanese Patent Application No. 2012-31823 for which it applied to Japan on February 16, 2012, and uses the content here.

  The present invention relates to a release agent emulsion composition, more particularly to a release agent emulsion composition for die casting, and more particularly to a release for die casting exhibiting good adhesion to the mold when applied to the mold. Agent emulsion composition.

  The release agent emulsion composition is usually used after being diluted several times with water and applied to a mold using a spray. As the release agent emulsion composition, for example, an acrylic silicone emulsion, an organo-modified silicone, a surfactant, and one or two selected from wax, fats and oils, mineral oil, synthetic ester oil and polyether-modified silicone are used. A mold release agent composition containing the same has been proposed (Japanese Patent Laid-Open No. 2004-18797).

  Further, the release agent composition with improved thermal stability is composed of dimethyl silicone oil and one or more of alkyl-modified silicone, phenyl-modified silicone, polyether-modified silicone, and carboxyl-modified silicone. A release agent composition in which a paintable silicone oil is mixed has been proposed (Japanese Patent Laid-Open No. 2003-48218).

Japanese Patent Laid-Open No. 2004-18797 JP 2003-48218 A

  However, in particular, in die casting production, the release agent emulsion composition is applied to a high-temperature mold, so that most of the applied emulsion composition does not adhere to the mold, and it will be repelled or run off. There was a problem. Further, when the viscosity of the base oil is increased in order to improve the adhesion to the mold, there is a problem that the emulsifiability deteriorates.

  The present invention has been made to solve the above-mentioned problems, and provides a release agent emulsion composition that is excellent in adhesion particularly when applied to a high-temperature mold and that has good mold-release properties. Objective.

As a result of intensive studies aimed at achieving the above object, the present inventors have reached the present invention. That is, the object of the present invention is to
(A) an alkyl group having 6 or more carbon atoms and an aralkyl group-containing organopolysiloxane,
This is achieved by a die-casting release agent emulsion composition comprising (B) a polyether group-containing organopolysiloxane and (C) water.

  The release agent emulsion composition for die casting of the present invention may further contain (D) a surfactant (excluding the component (B)).

（式中、
Ｒ’は、それぞれ独立して、炭素数１〜５の１価飽和脂肪族炭化水素基、炭素数２〜１０の１価不飽和脂肪族炭化水素基または炭素数６〜２０の１価芳香族炭化水素基であり、
Ｒ２は、それぞれ独立して、炭素数６〜２０のアルキル基であり、
Ｒ３は、それぞれ独立して、炭素数７〜２０のアラルキル基であり、
Ａ２は、それぞれ独立して、Ｒ’、Ｒ２またはＲ３であり、
ｘ、ｙおよびｚは任意の数であり、ｘ／（ｘ＋ｙ＋ｚ）＝０．７０以下、ｙ／（ｘ＋ｙ＋ｚ）＝０．１０以上、ｚ／（ｘ＋ｙ＋ｚ）＝０．１０以上を満たす数である）
で表されるアルキル基およびアラルキル基含有オルガノポリシロキサンであることが好ましい。The component (A) is represented by the following formula (2):

(Where
R ′ each independently represents a monovalent saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, or a monovalent aromatic group having 6 to 20 carbon atoms. A hydrocarbon group,
Each R2 is independently an alkyl group having 6 to 20 carbon atoms;
Each R3 is independently an aralkyl group having 7 to 20 carbon atoms;
Each A2 is independently R ′, R2 or R3;
x, y and z are arbitrary numbers, and satisfy x / (x + y + z) = 0.70 or less, y / (x + y + z) = 0.10 or more, and z / (x + y + z) = 0.10 or more)
It is preferable that it is the alkyl group and aralkyl group containing organopolysiloxane represented by these.

  In the above formula (2), x, y and z are x / (x + y + z) = 0.10 to 0.70, y / (x + y + z) = 0.10 to 0.80, z / (x + y + z) = 0. A number satisfying 10 to 0.80 is more preferable.

（式中、
Ｒは、それぞれ独立して、炭素数１〜２０の１価炭化水素基であり、
Ｒ１は、式：−（ＣＨ_２）_ｏ−（ＯＣ_２Ｈ_４）_ｐ−（ＯＣＨ_２ＣＨ（ＣＨ_３））_ｑ−Ｂ（Ｂは、Ｈ、ＯＨ、ＯＲ、ＣＯＯＨ、ＣＯＯＲまたはＯＣＯＲを表し、ｏは０〜４であり、ｐは０〜１００であり、ｑは０〜１００であり、ｐ＋ｑは２〜１００である）で表されるポリオキシアルキレン基であり、
Ａ１は、それぞれ独立して、ＲまたはＲ１であり、
ｍは１〜５００であり、
ｎは０〜１００であり、ただし、ｎ＝０のとき少なくとも１つのＡ１はＲ１である）
で表されるポリエーテル基含有オルガノポリシロキサンから選択される１種または２種以上の組合せであることが好ましい。The component (B) is represented by the following formula (1):

(Where
Each R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms;
R1 represents the formula: — (CH ₂ ) _o — (OC ₂ H ₄ ) _p — (OCH ₂ CH (CH ₃ )) _q —B (B represents H, OH, OR, COOH, COOR or OCOR; o is 0 to 4, p is 0 to 100, q is 0 to 100, and p + q is 2 to 100).
Each A1 is independently R or R1,
m is 1 to 500;
n is 0 to 100, provided that when n = 0, at least one A1 is R1)
It is preferable that it is 1 type, or 2 or more types of combinations selected from the polyether group containing organopolysiloxane represented by these.

  In the formula (1), p is 0 to 50, q is 0 to 50, p + q is 10 to 50, m is 5 to 200, and n is more preferably 0 to 20. .

  ADVANTAGE OF THE INVENTION According to this invention, the mold release agent emulsion composition for die castings which is excellent in the adhesiveness to the metal mold | die especially at high temperature, and has favorable mold release property can be provided.

The release agent emulsion composition for die casting of the present invention comprises:
(A) an alkyl group having 6 or more carbon atoms and an aralkyl group-containing organopolysiloxane,
It comprises (B) a polyether group-containing organopolysiloxane, and (C) water.

（式中、
Ｒ’は、それぞれ独立して、炭素数１〜５の１価飽和脂肪族炭化水素基、炭素数２〜１０の１価不飽和脂肪族炭化水素基または炭素数６〜２０の１価芳香族炭化水素基であり、
Ｒ２は、それぞれ独立して、炭素数６〜２０のアルキル基であり、
Ｒ３は、それぞれ独立して、炭素数７〜２０のアラルキル基であり、
Ａ２は、それぞれ独立して、Ｒ’、Ｒ２またはＲ３であり、
ｘ、ｙおよびｚは任意の数であり、ｘ／（ｘ＋ｙ＋ｚ）＝０．７０以下、ｙ／（ｘ＋ｙ＋ｚ）＝０．１０以上、ｚ／（ｘ＋ｙ＋ｚ）＝０．１０以上を満たす数である）
で表されるアルキル基およびアラルキル基含有オルガノポリシロキサンであってもよい。The (A) component alkyl group having 6 or more carbon atoms and the aralkyl group-containing organopolysiloxane are not particularly limited as long as the organopolysiloxane contains an alkyl group and aralkyl group having 6 or more carbon atoms in the molecular structure. It is preferable that it is a C6-C20 alkyl group and aralkyl group containing organopolysiloxane. For example, the following formula (2):

(Where
R ′ each independently represents a monovalent saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, or a monovalent aromatic group having 6 to 20 carbon atoms. A hydrocarbon group,
Each R2 is independently an alkyl group having 6 to 20 carbon atoms;
Each R3 is independently an aralkyl group having 7 to 20 carbon atoms;
Each A2 is independently R ′, R2 or R3;
x, y and z are arbitrary numbers, and satisfy x / (x + y + z) = 0.70 or less, y / (x + y + z) = 0.10 or more, and z / (x + y + z) = 0.10 or more)
Or an alkyl group-containing aralkyl group-containing organopolysiloxane.

  The monovalent saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms of R ′ in the formula (2) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , An isobutyl group, an alkyl group such as a pentyl group; a cycloalkyl group such as a cyclopentyl group; and a hydrogen atom bonded to a carbon atom of these groups is at least partially a halogen atom such as a fluorine atom, an epoxy group, a glycidyl group, And a group substituted with an organic group containing a functional group selected from the group consisting of an acyl group, a carboxyl group, an amino group, a methacryl group, and a mercapto group.

  The monovalent unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms of R ′ in the formula (2) is not particularly limited, and examples thereof include a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1- Linear or branched alkenyl groups such as butenyl, 2-butenyl, and hexenyl; cycloalkenyl such as cyclopentenyl and cyclohexenyl; cyclopentenylethyl, cyclohexenylethyl, and cyclohexenylpropyl Cycloalkenylalkyl groups such as groups; alkynyl groups such as ethynyl groups and propargyl groups; and the hydrogen atoms bonded to the carbon atoms of these groups are at least partially halogen atoms such as fluorine atoms, epoxy groups, glycidyl groups, acyls Group consisting of a group, a carboxyl group, an amino group, a methacryl group, and a mercapto group It includes substituted groups with an organic group containing a functional group al selected.

  The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of R ′ in the formula (2) is not particularly limited. For example, an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; a benzyl group Aralkyl groups such as, and the like, and hydrogen atoms bonded to carbon atoms of these groups are at least partially from halogen atoms such as fluorine atoms, epoxy groups, glycidyl groups, acyl groups, carboxyl groups, amino groups, methacryl groups, mercapto groups And a group substituted with an organic group containing a functional group selected from the group consisting of:

  R 'of the alkyl group and aralkyl group-containing organopolysiloxane represented by the formula (2) is preferably at least 50% methyl group, particularly preferably all methyl groups in terms of releasability. .

  The alkyl group having 6 to 20 carbon atoms of R2 in the formula (2) is not particularly limited. For example, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group , Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like; and halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom in which the hydrogen atom bonded to the carbon atom of these groups is at least partially And a group substituted with.

  The aralkyl group having 7 to 20 carbon atoms of R3 in the formula (2) is not particularly limited, but for example, benzyl group, 4-methylbenzyl group, p-methoxybenzyl group, diphenylmethyl group, 2-phenylethyl group, 2 -Phenylpropyl group, 3-phenylpropyl group, etc. are mentioned.

  A2 in the formula (2) is R ′, R2 or R3, and is preferably R ′.

  X, y and z in the formula (2) may be any number, but x is in the range of 0 to 250, particularly in the range of 0 to 200, and y is in the range of 1 to 100, in particular 10 to 80. And z is preferably in the range of 1 to 100, and more preferably in the range of 10 to 80. If the value of x + y + z is too large, the viscosity becomes too high and emulsification becomes difficult. Therefore, the value of x + y + z is preferably 300 or less.

  Further, the value of x / (x + y + z) in the formula (2) is preferably 0.70 or less from the viewpoint of paintability, and is further 0 from the viewpoint of heat resistance, releasability and ease of viscosity adjustment. More preferably, it is in the range of .10 to 0.70. The values of y / (x + y + z) and z / (x + y + z) are each preferably 0.10 or more from the viewpoint of paintability, and more preferably in the range of 0.10 to 0.80. When the values of x / (x + y + z), y / (x + y + z), and z / (x + y + z) are within the above ranges, the release agent at high temperatures tends to be excellent.

The values of x, y, and z can be determined by ²⁹ Si-NMR and ¹³ C-NMR.

  The arrangement of each siloxane structural unit of the formula (2) is not particularly limited, and may be random or block.

Preferably the kinematic viscosity at 25 ° C. of the silicone compound represented by the formula (2) is 500~10000mm ² / s, particularly preferably 1000~8000mm ² / s. This is because when the kinematic viscosity is lower than the above range, the silicone adhering to the heated mold is likely to flow off, and it is difficult to obtain good release properties. This is because it becomes difficult to obtain a stable emulsion.

  Although the silicone compound represented by Formula (2) can be used individually by 1 type, it can also be used in mixture of 2 or more types.

  As the component (A), only an alkyl group and aralkyl group-containing organopolysiloxane having 6 or more carbon atoms can be used, or an alkyl group-containing organopolysiloxane and an alkyl group and aralkyl group-containing organopolysiloxane having 6 or more carbon atoms. Can be used in combination.

（式中、Ｒ’およびＲ２は前述のとおりであり、Ａ３はＲ’またはＲ２であり、ａおよびｂは任意の数である）
で表されるアルキル基含有オルガノポリシロキサンであってもよい。The alkyl group-containing organopolysiloxane which may be used in combination with the (A) component alkyl group having 6 or more carbon atoms and the aralkyl group-containing organopolysiloxane may be an organopolysiloxane having an alkyl group in its molecular structure. For example, the following formula (3):

Wherein R ′ and R2 are as described above, A3 is R ′ or R2, and a and b are any numbers.
The alkyl group containing organopolysiloxane represented by these may be sufficient.

  Although a and b in Formula (3) can be made into arbitrary numbers, it is preferable that a is the range of 0-200 and b is the range of 1-200 from the point of paintability. If the value of a + b is too large, the viscosity becomes too high and emulsification becomes difficult. Therefore, the value of a + b is preferably 300 or less.

  The arrangement of each siloxane structural unit of the formula (3) is not particularly limited, and may be random or block.

Preferably the kinematic viscosity at 25 ° C. of the silicone compound represented by the formula (3) is 500~10000mm ² / s, particularly preferably 1000~8000mm ² / s. This is because when the kinematic viscosity is lower than the above range, the silicone adhering to the heated mold is likely to flow off, and it is difficult to obtain good release properties. This is because it becomes difficult to obtain a stable emulsion.

  Although the compound of Formula (3) can be used individually by 1 type, it can also be used in mixture of 2 or more types.

  In the emulsion composition for die casting of the present invention, the component (A) is dispersed in the form of droplets in water. The average particle size of the droplets is preferably in the range of 1 to 2000 nm, more preferably in the range of 10 to 1000 nm, and particularly preferably in the range of 10 to 400 nm. This is because when the average particle size is within the above range, the stability of the obtained emulsion is improved.

  Although content of (A) component is not specifically limited, It is preferable that it exists in the range of 0.1-90 mass parts with respect to 100 mass parts of mold release agent emulsion compositions for die-casting, and is 10-70 mass parts. It is particularly preferable that it is within the range.

  The (B) component polyether group-containing organopolysiloxane is not particularly limited as long as it is an organopolysiloxane having a polyether group in its molecular structure, and the polyether group may be a side chain, one end, or both ends. Alternatively, it may be an organopolysiloxane having a structure bonded to both side chains and both ends. Further, it may be a block copolymer type polyether group and alkyl group-containing organopolysiloxane.

（式中、
Ｒは、それぞれ独立して、炭素数１〜２０の１価炭化水素基であり、
Ｒ１は、式：−（ＣＨ_２）_ｏ−（ＯＣ_２Ｈ_４）_ｐ−（ＯＣＨ_２ＣＨ（ＣＨ_３））_ｑ−Ｂ（Ｂは、Ｈ、ＯＨ、ＯＲ、ＣＯＯＨ、ＣＯＯＲまたはＯＣＯＲを表し、ｏは０〜４であり、ｐは０〜１００であり、ｑは０〜１００であり、ｐ＋ｑは２〜１００である）で表されるポリオキシアルキレン基であり、
Ａ１は、それぞれ独立して、ＲまたはＲ１であり、
ｍは１〜５００であり、
ｎは０〜１００であり、ただし、ｎ＝０のとき少なくとも１つのＡ１はＲ１である）
で表されるポリエーテル基含有オルガノポリシロキサンから選択される１種または２種以上の組合せであってもよい。The polyether group-containing organopolysiloxane of component (B) is, for example, the following formula:

(Where
Each R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms;
R1 represents the formula: — (CH ₂ ) _o — (OC ₂ H ₄ ) _p — (OCH ₂ CH (CH ₃ )) _q —B (B represents H, OH, OR, COOH, COOR or OCOR; o is 0 to 4, p is 0 to 100, q is 0 to 100, and p + q is 2 to 100).
Each A1 is independently R or R1,
m is 1 to 500;
n is 0 to 100, provided that when n = 0, at least one A1 is R1)
1 type, or 2 or more types of combinations selected from the polyether group containing organopolysiloxane represented by these may be sufficient.

  In R1 of Formula (1), p is 0 to 50, q is 0 to 50, and p + q is preferably 10 to 50. More preferably, p + q is 20-50.

  M and n in formula (1) can be any number, but m is preferably in the range of 1 to 500 and n is preferably in the range of 0 to 100 from the viewpoint of productivity and handleability. Further, m is more preferably in the range of 5 to 200, and n is preferably in the range of 0 to 20. If the value of m + n is too large, the viscosity becomes too high, and the productivity and handleability, and further the emulsifiability and dispersibility in the emulsion composition are lowered. Therefore, the value of m + n is preferably 600 or less.

  The arrangement of each siloxane structural unit of formula (1) is not particularly limited, and may be random or block.

  The arrangement of the structural units of the polyoxyalkylene group represented by R1 in the formula (1) is not particularly limited, and may be random or block.

Preferably the kinematic viscosity at 25 ° C. of the polyether group-containing organopolysiloxane of the component (B) is a 100~10000mm ² / s, particularly preferably 500~8000mm ² / s. This is because when the kinematic viscosity is lower than the above range, the silicone adhering to the heated mold is likely to flow off, and it is difficult to obtain good release properties. On the other hand, when the kinematic viscosity is higher than the above range, the emulsion composition This is because the emulsifiability and dispersibility in the medium decrease.

  (B) The polyether group containing organopolysiloxane of a component can be used individually by 1 type, However, 2 or more types can also be mixed and used.

  (B) Although content of the polyether group containing organopolysiloxane of a component is not specifically limited, It is in the range of 0.1-20 mass parts with respect to 100 mass parts of mold release agent emulsion compositions for die-casting. A range of 0.5 to 10 parts by mass is particularly preferable.

  (C) Although content of the water of a component is not specifically limited, It is preferable to exist in the range of 10-99 mass parts with respect to 100 mass parts of mold release agent emulsion compositions for die-casting, and 30-80 mass parts is preferable. It is particularly preferable that it is within the range.

  The release agent emulsion composition for die casting of the present invention may further contain (D) a surfactant (excluding the component (B)). The surfactant is not particularly limited, but can be selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant. Surfactants may be used alone or in combination of two or more.

  Examples of the anionic surfactant include saturated or unsaturated fatty acid salts (for example, sodium laurate, sodium stearate, sodium oleate, sodium linolenate, etc.), alkyl sulfates, alkyl benzene sulfonic acids (for example, hexyl benzene sulfone). Acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc.) and salts thereof, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyethylene alkyl sulfate ester, sulfosuccinic acid alkyl ester salt, polyoxyalkylene Sulfosuccinic acid alkyl ester salt, polyoxyalkylene alkyl phenyl ether sulfate, alkane sulfonate, octyltrimethylammonium hydroxide, dodecylto Methyl ammonium hydroxide, alkyl sulfonate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl ether acetate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, acyl glutamate, α-acyl sulfonate, Alkyl sulfonate, alkyl aryl sulfonate, α-olefin sulfonate, alkyl naphthalene sulfonate, alkane sulfonate, alkyl or alkenyl sulfate, alkyl amide sulfate, alkyl or alkenyl phosphate, alkyl amide phosphorus Acid salt, alkyloylalkyl taurine salt, N-acyl amino acid salt, sulfosuccinate, alkyl ether carboxylate, amide ether carboxylate, α-sulfo fatty acid ester salt, ara Emissions derivatives, glycine derivatives, arginine derivatives and the like. Examples of the salt include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts.

  Examples of cationic surfactants include alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl bromide. Trimethylammonium, distearyldimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di (POE) oleylmethylammonium chloride (2EO), benzalkonium chloride, alkylbenzalkonium chloride, alkyldimethylbenzalkonium chloride, Benzethonium chloride, stearyldimethylbenzylammonium chloride, lanolin-derived quaternary Numonium salt, diethylaminoethylamide stearate, dimethylaminopropylamide stearate, amidopropyldimethylhydroxypropylammonium chloride, stearoylcholaminoformylmethylpyridinium chloride, cetylpyridinium chloride, tall oil alkylbenzylhydroxyethylimidazolinium chloride, benzyl An ammonium salt etc. are mentioned.

  Examples of the nonionic surfactant include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (curing) ) Castor oils, polyoxyalkylene alkylphenols, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyls Esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbit fatty acid esters, polyoxy Lucylene glycerin fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxyalkylene fatty acid bisphenyl ethers, polypropylene glycol, diethylene glycol, polyglyceryl modified silicone Glyceryl-modified silicone, sugar-modified silicone, fluorine-based surfactant, polyoxyethylene / polyoxypropylene block polymer, alkyl polyoxyethylene / polyoxypropylene block polymer ether, and the like.

  Examples of amphoteric surfactants include imidazoline type, amide betaine type, alkyl betaine type, alkyl amide betaine type, alkyl sulfobetaine type, amide sulfobetaine type, hydroxysulfobetaine type, carbobetaine type, phosphobetaine type, aminocarboxylic type Examples include acid type and amide amino acid type amphoteric surfactants. Specifically, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc. Imidazoline-type amphoteric surfactants; alkylbetaine-type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine and myristylbetaine; palm oil fatty acid amidopropyldimethylaminoacetic acid betaine, palm kernel fatty acid amidopropyldimethylaminoacetic acid betaine, beef tallow fatty acid amidopropyl Dimethylaminoacetic acid betaine, hardened beef tallow fatty acid amidopropyl dimethylaminoacetic acid betaine, lauric acid amidopropyl dimethylaminoacetic acid betaine, myristic acid amidopropyl dimethylaminoacetic acid betaine, palmitic acid amido Amidobetaine-type amphoteric surfactants such as pyrdimethylaminoacetic acid betaine, stearic acid amidopropyldimethylaminoacetic acid betaine, oleic acid amidopropyldimethylaminoacetic acid betaine; and alkylsulfobetaine-type amphoteric surfactants such as coconut oil fatty acid dimethylsulfopropyl betaine Alkylalkylsulfobetaine-type amphoteric surfactants such as lauryldimethylaminohydroxysulfobetaine; phosphobetaine-type amphoteric surfactants such as laurylhydroxyphosphobetaine; N-lauroyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine sodium N-oleoyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine sodium, N-cocoyl-N′-hydroxyethyl-N′-carboxymethyl Sodium ethylenediamine, N-lauroyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine potassium, N-oleoyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine potassium, N-lauroyl-N-hydroxyethyl-N '-Carboxymethylethylenediamine sodium, N-oleoyl-N-hydroxyethyl-N'-carboxymethylethylenediamine sodium, N-cocoyl-N-hydroxyethyl-N'-carboxymethylethylenediamine sodium, N-lauroyl-N-hydroxyethyl -N ', N'-dicarboxymethylethylenediamine monosodium, N-oleoyl-N-hydroxyethyl-N', N'-dicarboxymethylethylenediamine monosodium, N-cocoyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine monosodium, N-lauroyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine disodium, N-oleoyl-N Amide amino acid type amphoteric surfactants such as -hydroxyethyl-N ', N'-dicarboxymethylethylenediamine disodium, N-cocoyl-N-hydroxyethyl-N', N'-dicarboxymethylethylenediamine disodium The

  Examples of the semipolar surfactant include alkylamine oxide type surfactants, alkylamine oxides, alkylamidoamine oxides, alkylhydroxyamine oxides, and the like. Alkyldimethylamine oxide having 10 to 18 carbon atoms, 8 carbon atoms ~ 18 alkoxyethyldihydroxyethylamine oxide and the like are preferably used. Specifically, dodecyldimethylamine oxide, dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl Dimethylamine oxide, cetyldimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, isostearyl dimethylamine oxide, palm Fatty acid alkyl dimethylamine oxide, amidopropyl caprylate Methylamine oxide, capric acid amidopropyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, isostearic acid amidopropyl dimethylamine Oxide, oleic acid amidopropyl dimethylamine oxide, ricinoleic acid amidopropyl dimethylamine oxide, 12-hydroxystearic acid amidopropyl dimethylamine oxide, palm fatty acid amidopropyl dimethylamine oxide, palm kernel oil fatty acid amidopropyl dimethylamine oxide, castor oil fatty acid Amidopropyldimethylamine oxide , Lauric acid amidoethyl dimethylamine oxide, myristic acid amidoethyl dimethylamine oxide, palm fatty acid amidoethyl dimethylamine oxide, lauric acid amidoethyl diethylamine oxide, myristic amidoethyl diethylamine oxide, coconut fatty acid amidoethyl diethylamine oxide, lauric acid amidoethyl Examples thereof include dihydroxyethylamine oxide, myristic acid amidoethyl dihydroxyethylamine oxide, and coconut fatty acid amidoethyl dihydroxyethylamine oxide.

  The content of the surfactant as the component (D) is not particularly limited, but is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the release agent emulsion composition for die casting. A range of 5 to 10 parts by mass is particularly preferable.

  The mold release agent emulsion composition for die casting of the present invention is an emulsion composition containing the above components (A) to (C), and optionally (D) component. In addition to these components, other diorganopolyesters are used. Siloxane may be included.

  As a method for producing the release agent emulsion composition for die casting of the present invention, for example, the above-mentioned component (A) and component (B) can be prepared by using a conventional method using an emulsifier such as a homomixer, colloid mill, line mixer, homogenizer and the like. (C) The method of emulsifying in a component is mentioned. The polyether group-containing organopolysiloxane (B) can also be added after emulsifying the component (A) and other components in the component (C).

  In addition to the above components (A) to (D), the release agent emulsion composition for die casting of the present invention is an additive that is usually used as a release agent emulsion composition containing a silicone compound as another component, for example, Any one or more kinds of pH adjusters, preservatives, antifungal agents, rust preventives, colorants, mineral oils, higher fatty acids, thickeners, aluminum powders, graphite and the like are added unless the object of the present invention is impaired. Can be blended.

  The release agent emulsion composition for die casting of the present invention is sprayed uniformly on a mold using, for example, a spray gun, or a cloth, paper or brush impregnated with the release agent emulsion composition for die casting of the present invention is used. Used by applying to mold.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, all parts mean parts by mass. In addition, this invention is not limited by these Examples.

(Alkyl group and aralkyl group-containing organopolysiloxane)
The following alkyl group and aralkyl group-containing organopolysiloxane A and aralkyl group-containing organopolysiloxane B were used. These organopolysiloxanes were prepared by subjecting the corresponding methyl hydrogen polysiloxanes to a hydrosilylation reaction with alphamethylstyrene followed by a further hydrosilylation reaction with an alkene.

Organopolysiloxane A containing alkyl group and aralkyl group

Aralkyl group-containing organopolysiloxane B

(Polyether group-containing organopolysiloxane)
The following polyether group-containing organopolysiloxane C and polyether group-containing organopolysiloxane D were used. These polyether group-containing organopolysiloxanes were prepared by subjecting the corresponding methyl hydrogen polysiloxane to a hydrosilylation reaction with a polyoxyalkylene having an allyl ether group.

Polyether group-containing organopolysiloxane C

Polyether group-containing organopolysiloxane D

[Example 1]
50 parts of alkyl group and aralkyl group-containing organopolysiloxane A, 3.5 parts of polyoxyethylene (7 mol) propyl heptyl ether (HLB12.9), 0.5 parts of polyether group-containing organopolysiloxane C, polyoxyethylene ( 3 mol) 0.025 part of sodium lauryl sulfate and 4.43 parts of water were mixed and emulsified using a continuous mixer. Dilution was performed by adding 41.44 parts of water, 0.005 part of sodium bicarbonate was added as a pH adjuster, and a preservative was further added to obtain a milky white emulsion having a particle size of 236 nm.

[Example 2]
50 parts of alkyl group and aralkyl group-containing organopolysiloxane A, 3.5 parts of polyoxyethylene (7 mol) propyl heptyl ether (HLB12.9), 0.5 parts of polyether group-containing organopolysiloxane D, polyoxyethylene ( 3 mol) 0.025 part of sodium lauryl sulfate and 4.43 parts of water were mixed and emulsified using a continuous mixer. Dilution was carried out by adding 41.44 parts of water, 0.005 part of sodium bicarbonate was added as a pH adjuster, and a preservative was further added to obtain a milky white emulsion having a particle size of 235 nm.

[Example 3]
50 parts of alkyl group and aralkyl group-containing organopolysiloxane A, 2.0 parts of polyoxyethylene (7 mol) propyl heptyl ether (HLB12.9), 2.0 parts of polyether group-containing organopolysiloxane D, polyoxyethylene ( 3 mol) 0.025 part of sodium lauryl sulfate and 4.43 parts of water were mixed and emulsified using a continuous mixer. 41.44 parts of water was added for dilution, 0.005 part of sodium bicarbonate was added as a pH adjuster, and a preservative was further added to obtain a milky white emulsion having a particle size of 254 nm.

[Comparative Example 1]
50 parts of alkyl group and aralkyl group-containing organopolysiloxane A, 4.0 parts of polyoxyethylene (7 mol) propyl heptyl ether (HLB12.9), 0.025 part of polyoxyethylene (3 mol) sodium lauryl sulfate, and water 4.43 parts were mixed and emulsified using a continuous mixing apparatus. Dilution was performed by adding 41.44 parts of water, 0.005 part of sodium bicarbonate was added as a pH adjuster, and a preservative was further added to obtain a milky white emulsion having a particle size of 216 nm.

[Comparative Example 2]
50 parts of alkyl group and aralkyl group-containing organopolysiloxane A, 3.5 parts of polyoxyethylene (7 mol) propyl heptyl ether (HLB 12.9), polyoxyethylene (3 mol) propyl heptyl ether (HLB 5.9) 5 parts, 0.025 part of polyoxyethylene (3 mol) sodium lauryl sulfate, and 4.43 parts of water were mixed and emulsified using a continuous mixing apparatus. Dilution was performed by adding 41.44 parts of water, 0.005 part of sodium bicarbonate was added as a pH adjuster, and a preservative was further added to obtain a milky white emulsion having a particle size of 222 nm.

[Comparative Example 3]
1. 50 parts of alkyl group and aralkyl group-containing organopolysiloxane A, 2.0 parts of polyoxyethylene (7 mol) propyl heptyl ether (HLB 12.9), polyoxyethylene (3 mol) propyl heptyl ether (HLB 5.9) 0 parts, 0.025 part of polyoxyethylene (3 mol) sodium lauryl sulfate, and 4.43 parts of water were mixed, and emulsified using a continuous mixing apparatus. 41.44 parts of water was added for dilution, 0.005 part of sodium bicarbonate was added as a pH adjuster, and a preservative was further added to obtain a milky white emulsion having a particle size of 225 nm.

[Comparative Example 4]
Aralkyl group-containing organopolysiloxane B 50.7 parts, polyoxyethylene (6 mol) isodecyl ether (HLB 12.9) 4.2 parts, polyoxyethylene (3 mol) sodium lauryl sulfate 0.025 parts, and water 5 90 parts were mixed and emulsified using a continuous mixer. Dilution was performed by adding 38.87 parts of water, 0.005 part of sodium bicarbonate was added as a pH adjuster, and sodium benzoate and preservative were further added to obtain a milky white emulsion having a particle size of 225 nm.

(Adhesion evaluation method)
The release agent emulsion composition diluted 50 times with water was placed in a pressurized tank of an automatic spray device, and the measurement conditions such as spray pressure were set (spray shape pressure: 0.16 MPa, mist size) Pressure: 0.56 MPa, spray pressure: 0.42 MPa). Next, a steel plate having a length of 100 mm, a width of 100 mm and a thickness of 3.5 mm was placed on the heater and allowed to stand at 200 ° C. for 20 minutes. (Distance 200 mm, spraying time 9 seconds). Then, after removing a steel plate from an apparatus and cooling to room temperature, the weight of the component adhering to the steel plate was measured and adhesiveness was evaluated.

(Releasability evaluation method)
As the mold release resistance evaluation, the mold release resistance of the mold release agent was evaluated by a Lub tester. Specifically, a 200 mm × 200 mm × 30 mm iron plate (material SKD61) heated to a temperature of 200 ° C. is spray-coated with a release agent emulsion composition diluted 150 times with water (spray pressure: 0.4 MPa, nozzle − After the distance between the steel plates: 200 mm, spraying time: 1 second, in the space defined by the ring body (inner diameter: 60 mm, height: 50 mm, material: SS400) on the iron plate coated with the release agent emulsion composition. Then, molten aluminum (product number: ADC12) at a temperature of 680 ° C. was poured and solidified to form a test piece. Thereafter, the mold release resistance of the cast product was evaluated by the sliding load when the ring body was moved along the iron plate. The smaller the sliding load, the lower the release resistance and the higher the release property.

  For the release agent emulsion compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4, adhesion and release properties were measured by the above methods. The measurement results are shown in Table 1 below.

  From Table 1, when the release agent emulsion composition for die castings of Examples 1 to 3 was used, the adhesion amount to the steel sheet exceeded 25 mg, indicating excellent adhesion, while Comparative Examples 1 to 4 were used. When the mold release agent emulsion composition for die casting was used, the adhesion amount to the steel sheet was less than 20 mg, indicating only low adhesion.

  When the tensile resistance value was measured for the release agent emulsion composition for die casting of Example 1 and Comparative Example 1 and the release properties were compared, the release agent emulsion composition for die casting of Example 1 was used. The results showed that the tensile resistance value was lower and the mold release was excellent.

Claims (6)

(A) an alkyl group having 6 or more carbon atoms and an aralkyl group-containing organopolysiloxane,
A release agent emulsion composition for die casting, comprising (B) a polyether group-containing organopolysiloxane and (C) water. (D) Surfactant (excluding component (B))
The mold release agent emulsion composition for die casting according to claim 1, further comprising: (B) component is following formula (1):

(Where
Each R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms;
R1 represents the formula: — (CH ₂ ) _o — (OC ₂ H ₄ ) _p — (OCH ₂ CH (CH ₃ )) _q —B (B represents H, OH, OR, COOH, COOR or OCOR; o is 0 to 4, p is 0 to 100, q is 0 to 100, and p + q is 2 to 100).
Each A1 is independently R or R1,
m is 1 to 500;
n is 0 to 100, provided that when n = 0, at least one A1 is R1)
The mold release agent emulsion composition for die casting according to claim 1 or 2, which is one or a combination of two or more selected from polyether group-containing organopolysiloxanes represented by formula (1).   In said Formula (1), p is 0-50, q is 0-50, p + q is 10-50, m is 5-200, and n is 0-20. 2. A mold release agent emulsion composition for die casting according to 1. The component (A) is represented by the following formula (2):

(Where
R ′ each independently represents a monovalent saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, or a monovalent aromatic group having 6 to 20 carbon atoms. A hydrocarbon group,
Each R2 is independently an alkyl group having 6 to 20 carbon atoms;
Each R3 is independently an aralkyl group having 7 to 20 carbon atoms;
Each A2 is independently R ′, R2 or R3;
x, y and z are arbitrary numbers, and satisfy x / (x + y + z) = 0.70 or less, y / (x + y + z) = 0.10 or more, and z / (x + y + z) = 0.10 or more)
The mold release agent emulsion composition for die casting according to any one of claims 1 to 4, wherein the composition is an organopolysiloxane containing an alkyl group and an aralkyl group represented by formula (1).   In the formula (2), x, y and z are x / (x + y + z) = 0.10 to 0.70, y / (x + y + z) = 0.10 to 0.80, z / (x + y + z) = 0. The mold release agent emulsion composition for die casting according to claim 5, which is a number satisfying 10 to 0.80.