JPH05177294A - Release agent composition for aluminum die casting - Google Patents

Abstract

PURPOSE:To obtain the release agent compsn. for aluminum die casting having an excellent release property and extreme pressure lubricating property by emulsifying a specific organo-polysiloxane and an extreme pressure lubricant of an org. compd. system at specific rations in water by an emulsifier. CONSTITUTION:The organo-polysiloxane expressed by formula (where R is <=7C univalent aliphat. hydrocarbon group or phenyl group; R<1> is >=8C alkyl group, aralkyl group; -R<2>COOH, -R<3>COOR<4>, -R<5>COOR<6>, (R<2>, R<3>, R<5> are bivalent hydrocarbon groups; R<4>, R<6> are univalent hydrocarbon groups), A is R or R<1>, x is an integer from 0 to 50 integer, y in an integer from 10 to 450, x+y=10 to 500, x<y) is emulsified at 100 pts.wt. and the extreme pressure lubricant of a sulfur-contg. compd. system, halogenated org. compd. or phosphorus-contg. org. compd. system at 0.5 to 500 pts.wt. in the water by using the emulsifier. Thus, the release agent compsn. for aluminum die casting of an emulsion type having the excellent preserving and mechanical stability together with the release property and the extreme pressure lubricating property is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion type release agent composition for aluminum die cast which has releasability and extreme pressure lubricity and is excellent in storage and mechanical stability.

[0002]

2. Description of the Related Art Organopolysiloxane modified with an alkyl group, an aralkyl group, a carboxyl group or a carboxylic acid ester group is widely used as a release agent in the automobile industry. However, although these organopolysiloxanes are excellent in mold release property, they have a drawback that they are inferior in extreme pressure lubricity, and they are not sufficiently satisfactory as mold release agents for aluminum die cast using complicated molds. Therefore, there has been a demand for the development of a mold release agent for aluminum die cast which is more excellent in mold releasability and has excellent extreme pressure lubricity. In other words, in aluminum die cast molding, high-temperature molten aluminum is injected into a complicated mold at high pressure, so if the mold release agent used here has low extreme pressure lubricity, the oil film strength (cracking in the oil film part) will occur. Occurs, and as a result, the mold releasability of the aluminum molded product and the hot running property of aluminum deteriorate, so a mold release agent with superior mold releasability and extreme pressure lubricity is required. It was said that.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have arrived at the present invention as a result of research for solving the above problems. That is, an object of the present invention is to provide a mold release agent composition for aluminum die cast which is excellent in mold releasability and also excellent in extreme pressure lubricity.

[0004]

[Means for Solving the Problem and Its Action] The above-mentioned object is represented by the formula (A).

[Chemical 2] [In the formula, R represents a monovalent aliphatic hydrocarbon group having 7 or less carbon atoms or a phenyl group (provided that at least 50 mol% of R in the molecule is a methyl group), and R ¹ represents 8 carbon atoms. The above alkyl groups or aralkyl groups or the formula -R
² COOH, -R ³ COOR ⁴ or -R ⁵ is a group represented by OOCR ⁶ (wherein R ² , R ³ and R ⁵ are divalent hydrocarbon groups, and R ⁴ and R ⁶ are 1 hydrocarbon) Is a group), A is R
Or R ¹ (provided that when x is 0, it is R), x is an integer of 0 to 50, y is an integer of 10 to 450,
x + y is an integer of 10 to 500, and x <y].
100 parts by weight (B) Sulfur-containing organic compound-based, halogenated organic compound-based or phosphorus-containing organic compound-based extreme pressure lubricant 0.5 to 50 parts by weight emulsified in water with an emulsifier This is achieved by the agent composition.

To explain this, it is used in the present invention.
The organopolysiloxane as the component (A) is the main component of the release agent composition of the present invention, and in the above formula, R is a monovalent hydrocarbon group having 7 or less carbon atoms, which includes a methyl group and an ethyl group. Basis,
Examples thereof include alkyl groups such as propyl group and butyl group; phenyl group, cyclohexyl group and vinyl group. At least 50 mol% of these Rs are preferably methyl groups, and more preferably 100% are methyl groups. R ¹ is an alkyl group or an aralkyl group having 8 or more carbon atoms, or a compound represented by the formula —R ² COO in order to improve paintability, releasability, and compatibility with other organic raw materials.
H, a group represented by -R ³ COOR ⁴ or -R ⁵ OOCR ^6. In the formula, R ² , R ³ and R ⁵ are divalent hydrocarbon groups, and R ⁴ and R ⁶ are monovalent hydrocarbon groups. From the viewpoint of paintability and compatibility with other organic substances, R ² , R ³ and R ⁵ are preferably alkylene groups, and the total number of carbon atoms in R ² , R ³ + R ⁴ and R ⁵ + R ⁶ is 10 or more. Is preferred. A is R or R ¹ and is R only when x is 0. Formula in the above formula

[Chemical 3] As the unit indicated by

[Chemical 4] (Wherein R ⁷ is an alkyl group or an aral group having 8 or more carbon atoms), a unit, a formula

[Chemical 5] (In the formula, R ² is the same as the above.),
formula

[Chemical 6] (In the formula, R ³ is the same as the above.),
formula

[Chemical 7] (In the formula, R ⁵ and R ⁶ are the same as described above.) Are exemplified, and two or three of these units may be present in the same molecule. If x is too large, the paintability will be poor and it will repel paints, so x is 0.
The range is from -50. y is 10 in terms of paintability
Or more, 450 or less from the viewpoint of emulsifying property, and (x +
When y) exceeds 500, the viscosity becomes too large and the emulsification becomes difficult. Therefore, (x + y) is within the range of 500,
From the paintability, x <y. Among R ¹ , the formulas —R ² COOH, —R ³ COOR ⁴ or —R ⁵ OOCR
A group represented by ⁶ , wherein R ² , R ³ and R ⁵ are alkylene groups, R ⁴ and R ⁶ are alkyl groups, and R ² and R ³ +
Organopolysiloxanes having 10 or more carbon atoms in R ⁴ and R ⁵ + R ⁶ are preferred because they are oriented on the mold surface and the releasability is further improved.

The organopolysiloxane represented by the above formula can be obtained, for example, by using a catalyst such as chloroplatinic acid in a methyl hydrogen polysiloxane or a dimethyl siloxane / methyl hydrogen siloxane copolymer, and for example, formula CH ₂ ═CH ( C
H ₂ ) ₁₀ CH ₃ α-olefin, styrene or α-methylstyrene, the formula CH ₂ = CH- (CH ₂ ) ₈ C
Unsaturated fatty acids represented by OOH, wherein CH ₂ = CH (CH _2)
8 COOC ₃ H ₇ or CH ₂ = CHCH ₂ OOC ₁₁ H ₂₃
It can be easily synthesized by adding unsaturated fatty acid esters represented by.

The extreme pressure lubricant as the component (B) used in the present invention is a component that not only imparts extreme pressure lubricity (oil film strength) to the composition of the present invention but also improves releasability. , Sulfur-containing organic compound-based, halogenated organic compound-based or phosphorus-containing organic compound-based extreme pressure lubricants. Here, the sulfur-containing organic compound has the formula

[Chemical 8] Sulfurized dipentene, represented by the formula

[Chemical 9] (In the formula, R is an alkyl group.) And the like, sulfurized fats and oils such as sulfurized spalm oil, and a formula

[Chemical 10] A dibenzyl disulfide represented by the formula: (CH ₃ ) ₃ C-
Sulfides such as jitteryarybutyl disulfide represented by S--S--C-(CH ₂ ) ₃ ;

[Chemical 11] (In the formula, R is an alkyl group.) And the like.

As the halogenated organic compound system, chlorinated hydrocarbons such as chlorinated paraffin and chlorinated naphthalene, methyltrichlorostearate [Cl ₃ C- (CH ₂ ) ₁₆ C
OCH ₃ ] and formula

[Chemical 12] And the like, chlorinated carboxylic acid derivatives such as dioctyl furoline date, dibutyl cutinate, etc .; iodine compounds such as benzyl iodide, hydrogen compounds having a perfluoroalkyl group, and the like.

The phosphorus-containing organic compound system is represented by the formula:

[Chemical 13] Tricresyl phosphate represented by (C
Examples include phosphates and phosphites such as triallyl phosphite represented by ₁₂ H ₂₅₀ ) ₂ POH.

These extreme pressure lubricants can be uniformly dissolved and dispersed in the organopolysiloxane of the component (A) by using a stirrer or the like if the form is liquid or paste. Further, when these extreme pressure lubricants are solid at room temperature, it is possible to uniformly disperse them after mixing with the component (A) under heating above the melting point and stirring. If the extreme pressure lubricant of component (B) is too small, the extreme pressure lubricity (oil film strength) will be insufficient.
If it is too large, the storage stability, dilution stability and mechanical stability of the emulsion will be impaired, and the relative concentration of the organopolysiloxane (A) component will decrease, resulting in insufficient releasability and a decrease in heat resistance. Therefore, the blending amount thereof is in the range of 0.5 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the organopolysiloxane as the component (A). It is of course possible to use two or more kinds of these extreme pressure lubricants in combination.

The release agent composition for aluminum die cast of the present invention is obtained by emulsifying the organopolysiloxane of the component (A) and the extreme pressure lubricant of the component (B) in water with an emulsifier. However, examples of the emulsifier used here include nonionic surfactants, anionic surfactants, and cationic surfactants. Examples of nonionic surfactants include polyoxyalkylene alkyl ethers,
Polyoxyalkylene alkylphenol ethers,
Examples include polyoxyalkylene alkyl esters, sorbitan alkyl esters, polyoxyalkylene sorbitan alkyl esters, polyethylene glycol, and polypropylene glycol.

As the cationic surfactant, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide. , Quaternary ammonium hydroxide such as dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide, coconut oil trimethylammonium hydroxide, and salts thereof.

Examples of anionic surfactants include higher fatty acids such as stearic acid, oleic acid and lauric acid, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzene. Alkylbenzenesulfonic acid such as sulfonic acid; CH ₃
(CH ₂ ) CH ₂ O (C ₂ H ₄ O) ₂ SO ₃ H, CH ₃ (C
_{H 2) 8 CH 2 O (} C 2 H 4 O) 8 SO 3 H, CH 3 (CH 2)
₁₉ CH ₂ O (C ₂ H ₄ O) ₄ SO ₃ H, CH ₃ (CH ₂ ) ₈ CH
_{2 CH 2 C 6 H 4 O} (C 2 H 4 O) 2 SO 3 Polyoxyethylene monoalkyl ether sulfuric Eruteru such as H; sodium salt and alkyl naphthyl sulfonic acid, potassium salt, lithium salt or an amine salt It is illustrated. Among the metal salts of higher fatty acids, alkali metal salts are particularly useful as auxiliary emulsifiers for enhancing extreme pressure lubricants. Such an emulsifier is generally used as a nonionic surfactant alone, a nonionic surfactant in combination with an anionic surfactant, or a nonionic surfactant in combination with a cationic surfactant.

The aluminum die cast release composition of the present invention comprises an organopolysiloxane of the component (A) and an extreme pressure lubricant of the component (B) emulsified in water. An antiseptic or antifungal agent and a rust preventive may be added and mixed. As such an additive, sodium salt or potassium salt of benzoic acid, sodium salt or potassium salt of sorbic acid,
Examples thereof include sodium salt, potassium salt, and sodium nitrite salt of dehydroacetic acid. A colorant, a mineral oil, a higher fatty acid, a thickener, an aluminum powder, graphite or the like may be added to the releasing composition for aluminum die cast of the present invention, as long as the object of the present invention is not impaired.

The aluminum die cast mold release emulsion composition of the present invention comprises, for example, 30 to 55% by weight of the organopolysiloxane (A) as the component and 2 to 2 of the extreme pressure lubricant.
10% by weight, 5 to 9% by weight of emulsifier, 0.3 to 0.5% by weight of antiseptic or antifungal agent and rust inhibitor, and 62.% of water.
It can be easily produced by blending in an amount of 7 to 27.5% by weight and then emulsifying and dissolving it using an emulsifying machine such as a homogenizer, a colloid mill, a line mixer, a homomixer or a sonolator. The aluminum die cast mold release emulsion composition of the present invention is generally used by spraying it uniformly onto the surface of the aluminum die cast mold using a spray machine.

[0016]

EXAMPLES Next, the present invention will be explained by examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight". The viscosity is a value at 25 ° C.

The structural formula and viscosity of the organopolysiloxane used in the examples are as follows.

[Chemical 14] The extreme pressure lubricants used in the examples are as follows. (A) Tricresyl phosphate

[Chemical 15] Dioctyl chlorene dating

[Chemical 16] (C) G-tert-butyl disulfide

[Chemical 17] (D) Jinkuji thiophosphite ADEKAKI CLUB Z-112: manufactured by Asahi Denka Co., Ltd. (e) Perfluoro compound (perfluoroalkylhydrochiric lipophilic oligomer) Megafac F-177: manufactured by Dainippon Ink and Chemicals, Inc.

In the examples and comparative examples, the organopolysiloxane emulsion compositions were evaluated for the following items by the following methods. ○ Paintability: An organopolysiloxane emulsion composition is diluted 50 times with water, uniformly sprayed onto clay-coated paper using a simple spray gun, dried at room temperature, and then ruled with an oil-based thick ink for thick writing. Using this method, the paper was drawn at equal intervals, and the appearance of faint lines was determined as follows. ◯: There was no blur of lines, and the magic ink adhered uniformly. Δ: There was a slight blurring of the line partially, and the non-uniform adhesion of the magic ink was observed. X: Line fading was remarkable. ○ Releasability: An organopolysiloxane emulsion composition diluted 5 times with water was sprayed onto a mold having an inner diameter of 5 cm × 5 cm, a depth of 5 mm, a bottom having unevenness and having many grooves, and then about 3 times.
Preheated to 50 ° C. Aluminum hot water melted at about 750 ° C. was poured into this mold and an electric furnace, and after cooling, an aluminum piece was peeled off from the mold and the releasability was evaluated by the degree of peeling. ⊚: Very good mold releasability ◯: Good mold releasability Δ: Slightly bad mold releasability ×: Die release is difficult ○ Emulsion storage stability: 200 cc of mayonnaise bottle with 18 parts of organopolysiloxane emulsion composition
Stability was investigated by putting 0 cc and leaving it at room temperature of 25 ° C. for 3 months. ○ Dilution stability of emulsion: Organopolysiloxane emulsion composition so that the organopolysiloxane concentration becomes 1% (organopolysiloxane concentration 50
% 50 times) diluted with tap water, 200cc at room temperature for 2 days
It was allowed to stand in the mayonnaise bottle, and the oil floating and cream generation were observed. ○ Mechanical stability of emulsion: The organopolysiloxane emulsion composition was diluted with tap water so that the concentration of the organopolysiloxane was 1%, and 50 ml was added to a 1l beaker.
After adding 0 cc and using a homomixer at a speed of 5000 rpm for 30 minutes, the mixture was placed on a beaker, and oil adhesion such as walls on the beaker and oil floating above the beaker were observed. ○ Extreme pressure lubricity of emulsion: The organopolysiloxane emulsion composition was measured under the following conditions according to the JISK-2519 lubricating oil load resistance test method, and the seizure load (Kg)
Was calculated. The specifications of the measurement model are as follows. Model and name: 4-ball friction tester (manufactured by Shinko Zoki Co., Ltd.) Test rope: Ball bearing rope 3/4 "(basic diameter 1
9.05 mm) High-grade JIS-B-1501 Load from test rope: Max. 1000 kg Vertical shaft rotation speed: 750 rpm Vertical shaft rotation direction: Clockwise when viewing the lower part from the upper part

[0019]

Example 1 4 parts of 50 parts of organopolysiloxane A and 5 kinds of extreme pressure lubrication a to e were added to 5 beakers each,
Stir evenly. Then, as an emulsifier, 4 parts of polyoxyethylene (6 mol) lauryl ether and polyoxyethylene (4.5 mol) lauryl sulfate sodium ester salt 1.
0 part was added and the mixture was stirred uniformly using a stirrer. Then
To this, 5 parts of water was added, and after stirring, the mixture was passed through a colloid mill type emulsifying machine to emulsify, then 36 parts of water was added and uniformly dissolved to prepare an organopolysiloxane emulsion composition. The results of measuring the properties of these compositions are shown in Table 1.

[0020]

Comparative Example 1 An organopolysiloxane emulsion composition was prepared in the same manner as in Example 1 except that the extreme pressure lubricant was not added. The characteristics of this composition were measured in the same manner as in Example 1. The results are also shown in Table 1. From the results shown in Table 1, the extreme pressure lubricity (seizure load) of the composition of the present invention was remarkably improved to about 1.6 times, and its releasability was extremely good.

[Table 1]

[0021]

Example 2 The same procedure as in Example 1 was carried out except that organopolysiloxane B, C or D was used in place of organopolysiloxane A and 4 parts of extreme pressure lubricant a was added to each. A polysiloxane emulsion composition was prepared. For comparison, an organopolysiloxane emulsion composition was prepared in the same manner as above except that the extreme pressure lubricant was not added. The properties of these compositions were measured as in Example 1. The results are shown in Table 2.

[Table 2]

[0022]

Example 3 In Example 1, 3.5 parts of extreme pressure lubricant a and 1.5 parts of extreme pressure lubricant e were used instead of extreme pressure lubricants a to e.
An organopolysiloxane emulsion composition was prepared in the same manner as in Example 1 except that the parts were used in combination. For comparison, an organopolysiloxane emulsion composition was prepared in the same manner as above except that the extreme pressure lubricant was not added. The properties of these compositions were measured in the same manner as in Example 1, and the results are shown in Table 3. From these results, the composition of the present invention has extremely high extreme pressure lubricity and good mold releasability, and was suitable as a mold release agent for aluminum die cast.

[Table 3]

[0023]

Example 4 In Example 1, 100 parts of the organopolysiloxane A was replaced with 0.1 part of the extreme pressure lubricant a instead of 4 parts.
An organopolysiloxane emulsion composition was prepared in the same manner as in Example 1, except that 1 part, 1 part, 5 parts, 10 parts, 25 parts, and 50 parts were added. For comparison, an organopolysiloxane emulsion composition was prepared in the same manner as above except that the extreme pressure lubricant was not added. The properties of these compositions were measured as in Example 1. The results are shown in Table 4. From these results, the composition of the present invention was well balanced and good as a release agent for aluminum die cast. However, in 0.1 part of the extreme pressure lubricant, the extreme pressure lubricant was insufficient. Further, when the amount added exceeds 50 parts, the storage stability of the emulsion is poor and it is unsuitable as a release agent for aluminum die cast.

[Table 4]

[0024]

The lubricant composition for aluminum die cast of the present invention comprises the organopolysiloxane (A) as the component.
Since the extreme pressure lubricant as the component (B) is emulsified in water with an emulsifier, it is characterized by being excellent in mold releasability and extreme pressure lubricity (oil film strength).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C10M 135: 22 137: 04 135: 34) C10N 30:00 A 8217-4H 30:06 40:24 A 8217-4H 40:36 8217-4H

Claims (1)

[Claims] 1. A formula (A): [In the formula, R represents a monovalent aliphatic hydrocarbon group having 7 or less carbon atoms or a phenyl group (provided that at least 50 mol% of R in the molecule is a methyl group), and R ¹ represents 8 carbon atoms. The above alkyl groups or aralkyl groups or the formula -R
² COOH, -R ³ COOR ⁴ or -R ⁵ is a group represented by OOCR ⁶ (wherein R ² , R ³ and R ⁵ are divalent hydrocarbon groups, and R ⁴ and R ⁶ are 1 hydrocarbon) Is a group), A is R
Or R ¹ (provided that when x is 0, it is R), x is an integer of 0 to 50, y is an integer of 10 to 450,
x + y is an integer of 10 to 500, and x <y].
100 parts by weight, (B) sulfur-containing organic compound-based, halogenated organic compound-based or phosphorus-containing organic compound-based extreme pressure lubricant 0.5 to 50 parts by weight is emulsified in water with an emulsifier to be used for aluminum die cast release. Mold composition.