JP3290540B2 - Release agent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release agent composition, in particular, a release agent which makes it possible to improve the mold release of a polyurethane molded product, not to hinder polyurethane foaming, and to maintain a good cell state. The present invention relates to an agent composition.

[0002]

2. Description of the Related Art It is easy to release a molded product from a mold when molding a molded product made of a resin such as an acrylic resin, an epoxy resin, a urethane resin, a vinyl chloride resin, a vinyl acetate resin, or a synthetic rubber. In order to do this, a mold release agent is applied to the inside of the mold. In many cases, a wax, soap and / or oil-based material is used as the mold release agent for this purpose. I have. However, polyurethane is widely used for adhesives because it has a strong adhesive strength to other materials, but it is particularly difficult to release it from the mold when manufacturing molded products. It has become something.

[0003] A polyethylene wax release agent has been proposed for this release (see Japanese Patent Publication No. 56-5844). However, this release agent has poor release performance, especially when continuous molding is performed. There are disadvantages in that the release agent accumulates in the mold, the release agent powder scatters and contaminates the surroundings, and the resulting molded article loses gloss. In addition, a release agent comprising aminosiloxane and dimethylpolysiloxane (see Belgian Patent No. 814909), an α-methylstyrene-modified dimethylpolysiloxane and MQ resin (a resin comprising triorganosiloxane units and SiO ₂₎ ) And a silicone release agent consisting of
However, since these release agents do not wet the mold uniformly, a part of the urethane resin remains in the mold and the peeling becomes heavy.

[0004] For this purpose, a release agent comprising a perfluoroalkyl phosphate and silicone is known (see JP-B-53-23270 and JP-B-53-23271). A composition comprising a perfluoroalkyl phosphate and a silicone varnish has also been proposed because it does not have a sufficiently satisfactory release performance (see JP-A-53-133490). However, there is a disadvantage that it is difficult to dissolve in water and the peeling is heavy.

[0005]

Therefore, a release agent containing MQ resin, an amino group-containing siloxane and a polyfluoroalkyl group-containing polymer has been proposed as having excellent release performance and good wettability. (Refer to Japanese Patent Publication No. 59-32514), however, all of these are used in the form dissolved in an aromatic hydrocarbon solvent or a chlorinated hydrocarbon solvent, so their flammability, toxicity, etc., have problems. Yes, this also has the disadvantage of impairing the uniformity of the polyurethane foam cells. In addition, although these are all solvent-based release agents, in order to prevent adverse effects on the environment in recent years, aqueous-based release agents, for example, release agents containing high molecular hydrocarbons as release components have been proposed. Examples thereof include aqueous dispersions of polyethylene wax, aqueous emulsions of paraffins and aqueous emulsions of emulsion polymers of unsaturated hydrocarbons, but these also do not have sufficient release performance.

On the other hand, the aqueous release agent comprises an aqueous release agent comprising a release agent such as a hydrocarbon polymer, silicone or wax, an emulsifier and an ethoxylated alcohol (see JP-A-4-298306). Aqueous release agents containing polyvinyl alcohol as a mold active substance and blended with a foaming stabilizer (see Japanese Patent Application Laid-Open No. 4-298307) have also been proposed, but these have improved the surface properties of polyurethane molded articles to some extent. , But it does not sufficiently satisfy the peeling performance.

[0007]

SUMMARY OF THE INVENTION The present invention is directed to an aqueous release agent composition which solves such disadvantages, disadvantages and problems and is suitable for an external release agent in polyurethane molding. Is (A) 1 to 15% by weight of wax, (B) formula R ¹
₃ SiO _1/2 unit, SiO ₂ unit, R ¹ ₂ SiO unit, R ¹ SiO _3/2 unit
(Where R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms)
Consists units-option, among these all the structural units R ¹ ₃ S
When the total amount of iO _1/2 unit and SiO ₂ unit is 80 mol% or more, this R
¹ ₃ in the range of molar ratio of SiO _1/2 units / SiO ₂ units 0.5 to 1.5
An organic solvent soluble silicone resin 10-30% by weight,
(C) Highly polymerized organopoly represented by the above formula (Formula 1)
White hexane and / or formula _{^{R 4 a R 5 b R 6}} c SiO (4-abc) / 2
[Where R ⁴ is -R ⁷ (NR ⁸ CH ₂ CH ₂ ) _n NR ⁹ R ¹⁰ (R ⁷ is carbon number
1 to 4 divalent hydrocarbon groups, R ⁸ , R ⁹ and R ¹⁰ are each
A hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is 0
≦ n ≦ 4), wherein R ⁵ is a carbon atom
1-8 unsubstituted or substituted monovalent hydrocarbon groups, R ⁶ is OR
R ¹¹ a hydroxyl group or an alkoxy group represented by ¹¹ hydrogen atoms
Or a monovalent hydrocarbon group having 1 to 6 carbon atoms, a, b, c
1.8 for 0.0001 ≦ a ≦ 1, 1.8 ≦ b ≦ 2.2, 0 ≦ c ≦ 0.1
<A + b + c <2.3], and the amine equivalent is 500 to 1
00,000 (g / mol), viscosity at 25 ° C is 10-100,000 cS
0.5 to 10% by weight of an amino group-containing organopolysiloxane , (D) 0.5 to 30% by weight of one or more emulsifiers selected from a nonionic emulsifier and an ionic emulsifier, and (E) a balance of water. The ratio of the total amount of the components (A) and (B) to the component (C) is [(A) + (B)].
/ (C) = 99/1 to 75/25.

That is, the present inventors have conducted various studies to develop a release agent composition used particularly in the production of a polyurethane molded product. As a result, this release agent was used for (A) wax and (B)
Silicone resin described in detail in the, (C) the <br/> high degree of polymerization has been described in detail in the organopolysiloxane and / or the
The amino group-containing organopolysiloxane described in detail , (D)
If it consists of an emulsifier, it shows excellent release properties, and when it is applied to the surface of a molding frame for the production of polyurethane moldings, it forms a film with the action of wax and silicone resin, It exhibits excellent release properties due to the action of the high polymerization degree polysiloxane and amino group-containing polysiloxane as release components. This has very little inhibition on urethane foaming. It has been found that they can be obtained as a good product, and the present inventors have completed the present invention by conducting research on the types and amounts of these components. This will be described in more detail below.

[0009]

The present invention relates to a release agent composition, which comprises (A) 1 to 15% by weight of a wax,
(B) The organic solvent-soluble silicone resin 10 described in detail above
30 wt%, (C) a high polymerization degree organopolysiloxane and / or) amino group-containing organopolysiloxane 0.5 to 10 wt% as detailed above as detailed above, (D) a nonionic emulsifier and an ionic 1 selected from emulsifiers
One or two or more emulsifiers in an amount of 0.5 to 30% by weight, (E) the remainder of water, and the ratio of the total amount of the components (A) and (B) to the component (C) is [(A) + (B )] / (C) = 99 /
1 to 75/25, which shows excellent release properties from the polyurethane molded article, and provides a good molded article without deteriorating the appearance of the polyurethane molded article. It has the advantage of giving.

[0010] The wax as the component (A) constituting the release agent composition of the present invention may be natural or montan wax, montanic acid ester wax, microcrystalline wax, paraffin wax, carnauba wax, bead wax, polyethylene wax or the like. It may be selected from synthetic waxes, and may be a mixture of one or more of these at a specific ratio.

These wax components have no or little reactivity with the urethane raw material, but they must be ones which do not impair the release performance, so that they are easily released and emulsified and dispersed in water. From the point of view, a montanic acid ester wax is preferred. If the compounding amount of this wax is less than 1% by weight with respect to the whole system, the film-forming property is not sufficient, and if it is more than 15% by weight, there is a problem of deposition on the urethane molding frame. It is required to be 1 to 15% by weight, but a preferable range is 5 to 5.
12% by weight.

Further, although constituting a release agent composition of the present invention (B) an organic solvent-soluble silicone resin as component also serves as the function of the film-forming and release properties expression, which is R ¹ ₃ SiO _1/2 units, SiO ₂ units, R ¹ ₂ SiO units, are made from units selected from R ¹ SiO _3/2 units. This R ¹
Is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a cycloalkyl group such as a cyclohexyl group; And it is preferable that 80 mol% or more of the monovalent hydrocarbon group is a methyl group.

[0013] Thus, in one of these units R ¹ ₃ Si
The O _1/2 unit and the SiO ₂ unit are important, and the total amount of these two units needs to be 80 mol% or more of the whole, and this is preferably 90 mol% or more. This R ¹ ₃ SiO _1/2
When the molar ratio of the unit / SiO ₂ unit is less than 0.5, when the film is formed into a film, the hardness is too high, and the deposition on the forming mold becomes a problem. When the molar ratio is larger than 1.5, the film is too soft, and the mold is released. This is required to be in the range of 0.5 to 1.5 because of the loss of persistence, but this preferred range is
0.6 to 1.2. When the amount of the component (B) is less than 10% by weight, the film formability is insufficient, and when the amount is more than 30% by weight, mold contamination is caused. The preferred range is 15-25% by weight
It is said.

Next, the component (C) constituting the release agent composition of the present invention is composed of a high polymerization degree organopolysiloxane and / or
Alternatively, it is an amino group-containing organopolysiloxane.
This high polymerization degree organopolysiloxane has the following general formula (1)

Embedded image Wherein R ² is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group, a phenyl group, An aryl group such as a tolyl group, or a chloromethyl group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with a halogen atom, a cyano group, or the like, a 3,3,3-trifluoropropyl group , A cyanoethyl group or the like, and preferably at least 90% of the group is a methyl group. The same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, Methyl group, ethyl group,
An atom or group selected from a vinyl group, a phenyl group, a hydroxyl group, and an alkoxy group, preferably a methyl group or a hydroxyl group, and m is 2,000 to 20,000 because this is a highly polymerized product. It is assumed to exhibit rubber-like properties.

Regarding this, dimethylpolysiloxane whose molecular chain ends are blocked with trimethylsilyl groups, dimethylpolysiloxane whose molecular chain ends are blocked with hydroxyl groups, and dimethylsiloxane and diphenylsiloxane whose molecular chain ends are blocked with trimethylsilyl groups Copolymers, copolymers of dimethylsiloxane and methylvinylsiloxane whose molecular chain ends are blocked with hydroxyl groups, dimethylsiloxane and methyl-3,3,3 containing vinyl groups at molecular chain ends
-Copolymers with trifluoropropylsiloxane.

The amino group-containing organopolysiloxane is represented by the following general formula (2): R ⁴ _a R ⁵ _b R ⁶ _c SiO _{(4-abc) / 2} (2) , Where R ⁴ is the formula -R ⁷ (NR ⁸ CH ₂ CH ₂ ) _n NR ⁹ R
Indicated by ^10, R ⁷ is a methylene group, an ethylene group, a propylene group, a divalent hydrocarbon group having 1 to 4 carbon atoms exemplified by butylene ^{group, R 8, R 9, R} 10 is a hydrogen atom or a methyl group An alkyl group such as ethyl group, propyl group, and butyl group; an alkenyl group such as vinyl group and allyl group; or a part or all of the hydrogen atoms bonded to carbon atoms of these groups are halogen atoms, cyano groups, and the like. And the same or different unsubstituted or substituted 1 to 4 carbon atoms selected from chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, etc.
R ⁵ is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group, alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group and tolyl group, and cyclo groups such as cyclohexyl group. A chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoro group in which some or all of the hydrogen atoms bonded to the carbon atoms of an alkyl group or these groups are substituted with a halogen atom, a cyano group, or the like; Propyl group,
Those with an unsubstituted or substituted monovalent hydrocarbon group of the same or a carbon number of heterologous 1-18 selected from such cyanoethyl group, preferably above its 90 mol% methyl, R ⁶
The hydroxyl group or an alkoxy group represented by the formula OR ^11, R ¹¹
Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms exemplified by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, particularly preferably a methyl group, a and b , C are respectively 0.0001 ≦ a ≦ 1, 1.8 ≦ b
≦ 2.2, 0 ≦ c ≦ 0.1 and 1.8 <a + b + c <2.3.

The amino group-containing organopolysiloxane may be branched, but is preferably a straight-chain, and is preferably an aqueous composition having an amine equivalent (g / mol) of less than 500. In addition to the fact that the product becomes poor in stability, it may react with the isocyanate of the urethane raw material to form a gel, and if it is larger than 100,000, sufficient releasability cannot be obtained. , Preferably in the range of 1,000 to 50,000. Further, when the viscosity is less than 10 cS, the stability of the emulsified composition is reduced, and the releasability of the polyurethane molded product is also reduced.When the viscosity is 100,000 cS or more, the emulsification becomes difficult. Although it is necessary to have a range of cS, the preferred range may be 50 to 10,000 cS, and the amino group-containing organopolysiloxane is represented by the following formula:

Embedded image (Where p to w are integers) are exemplified.

If the amount of the component (C) is less than 0.5% by weight with respect to the whole system, sufficient releasability cannot be obtained, and if the amount is more than 10% by weight, the urethane foam cannot be used. Since the foaming is hindered and the cells become more nonuniform, it is required to be in the range of 0.5 to 10% by weight, and the preferable range is 1 to 5% by weight.

The mixing ratio of the components (A), (B) and (C) is such that the total amount of the components (A) and (B) and the mixing ratio of the component (C) are [(A) + (B)] / (C) =
If the ratio is larger than 99/1, the peeling performance is reduced.
+ (B)] / (C) = 75/25, the urethane foam cells become non-uniform, so this is [(A) +
(B)] / (C) = 99/1 to 75/25, which is more preferably [(A) + (B)].
/ (C) = 95/5 to 80/20. The component (C) is a high polymerization degree organopolysiloxane and / or an amino group-containing organopolysiloxane,
These may be used singly or in combination, but since they all show substantially the same effect, it is not necessary to particularly define the mixing ratio of the two when they are used in combination. When the ratio of the component (A) to the component (B) is less than 20% by weight, the foam cell diameter tends to be non-uniform, and when the ratio is more than 60%, the releasability decreases. The weight ratio is preferably in the range of (A) / (B) = 20/80 to 60/40, and more preferably in the range of (A) / (B) = 30/70 to 50/50.

Next, the emulsifier as the component (D) constituting the release agent composition of the present invention is one or more selected from a nonionic emulsifier and an ionic emulsifier. Examples of the nonionic emulsifier include polyoxyethylene higher alcohol ether, polyoxyethylene alkyl phenyl ether, sorbitan monoalkylate, sorbitan trialkylate, polyoxyethylene sorbitan monoalkylate, polyoxyethylene sorbitan trialkylate, polyoxyethylene sorbitol tetraalkylate. Examples thereof include alkylates, glycerol monoalkylates, etc., which can be used alone or in combination of two or more. These include, in addition to these general nonionic emulsifiers, fluorine-based emulsifiers or silicone-based emulsifiers. A nonionic emulsifier can also be used, but it is preferable that this nonionic emulsifier has an HLB in the range of 1.5 to 20, preferably 7.0 to 15.0.

The ionic emulsifier includes anionic, cationic and amphoteric emulsifiers. Examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and dialkyl sulfo succinate. Sodium acid, potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc., and cationic emulsifiers such as cetyltrimethylammonium chloride and stearyltrimethylammonium chloride , Lauryltrimethylammonium chloride, stearylamine hydrochloride, coconutamine hydrochloride, cocona DOO amine acetate, stearylamine acetate, etc. alkylbenzene dimethyl ammonium chloride are exemplified.

Further, as the amphoteric emulsifier, N
-Acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxypropylammoniobetaines, and the like. The emulsifier may be any of these nonionic emulsifiers and ionic emulsifiers, or a mixture thereof. However, if the compounding amount is less than 0.5% by weight with respect to the whole system, it becomes difficult to emulsify and disperse. If the content is more than 30% by weight, the viscosity of the emulsified composition becomes high, the workability is impaired, and the peeling performance is also reduced. Therefore, it is necessary to set the range of 0.5 to 30% by weight. The range is between 1 and 20% by weight.

The release agent composition of the present invention is described in detail above for the wax as the component (A) and the wax as the component (B).
Organic solvent-soluble silicone resin, as component (C)
The high-polymerization degree organopolysiloxane described in detail above and / or the amino group-containing organopolysiloxane described in detail above are mixed, an emulsifier as a component (D) is added thereto, mixed, and water is added. This can be obtained as an O / W type emulsified composition by repeating (A)
The components (B) and (C) can also be obtained by mixing each of the components separately as an emulsified composition using an emulsifier.

In this case, when each of the components (A), (B) and (C) is separately made into an emulsified composition, the wax as the component (A) is emulsified while heating and dissolving using an anionic emulsifier. The silicone resin as the component (B) is preferably an aromatic hydrocarbon solvent such as toluene or xylene, a hydrocarbon solvent such as kerosene, petroleum, ether, ligroin, or isoparaffin, or a cyclic or linear volatile solvent. It is preferable to emulsify a substance dissolved in a silicone solvent or the like.

The emulsification of the organopolysiloxane having a high degree of polymerization as the component (C) can be carried out by benzene, toluene,
What is necessary is to emulsify and disperse an aromatic hydrocarbon solvent such as xylene, kerosene, petroleum ether, ligroin, a hydrocarbon solvent such as inparaffin, or a solution dissolved in a cyclic or linear low molecular weight silicone solvent. After emulsifying and dispersing a low molecular weight organopolysiloxane, polymerize it by adding a strong acid or strong alkali catalyst, or emulsify and disperse a low molecular weight organopolysiloxane using a surfactant having catalytic activity, An emulsion may be obtained by polymerization, and this (C)
The amino group-containing organopolysiloxane as a component may be emulsified by using a nonionic emulsifier as a main emulsifier.

The release agent composition of the present invention,
Alternatively, it may be used after appropriately diluting with water,
For this purpose, it is optional to add an antistatic agent, a preservative and a rust inhibitor to the range without significantly departing from the scope of the present invention. When the thus-produced release agent composition of the present invention is applied to the surface of a molding die for producing a polyurethane molded product, wax (A) is used as the component (A).
A film is formed here by the silicone resin as the component (B), and since the organopolysiloxane as the component (C) functions as a release component, it exhibits excellent release properties from the urethane molded article. Since the inhibition of urethane foaming is extremely small, the resulting urethane molded article can have a good cell state and a good appearance.

[0027]

EXAMPLES Next, examples of the synthesis of component emulsions (A), (B) and (C) used in Examples and Comparative Examples of the present invention, and Examples and Comparative Examples will be given. The measured values at 25 ° C. are shown, and the peeling force and foam cell diameter (uniformity) in the examples are the results obtained by the following methods. (Release force) A release agent is spray-coated on an epoxy plate (25 × 100 mm × 2 mm thick) and air-dried at room temperature for 30 minutes or more. Then, 3 g of a urethane foam stock solution having the following composition is dropped on the epoxy plate. Compressed at 70 ° C for 5 minutes and thickness approx.
Create a 1.5mm sheet urethane foam and fill it with 0.
The peeling force when peeled in the direction of 180 ° at a speed of 3 m / min was measured. <Urethane foam stock solution composition> Polyester polyol 68% by weight Toluene diisocyanate 28% by weight N-ethylmorpholine 1% by weight Blowing agent F-258 [trade name of Shin-Etsu Chemical Co., Ltd.] 0.7% by weight Water 2% by weight

(Foam cell diameter) 2 g of a release agent was added to 200 g of the above urethane foam-containing liquid, and 2,2 g was added using a homodisper.
Perform foam molding by mixing and stirring at room temperature for 20 seconds at 000 rpm, and then heat and cure at 100 ° C for 5 minutes to form urethane foam, then cut this urethane foam with a cutter and measure the average internal cell diameter did. The average cell diameter of the urethane foam without adding a release agent is about 30
8080 μm.

<Preparation of Component (A) Emulsion> (A-1) 15 g of morpholine and 785 g of deionized water were placed in a flask equipped with an anchor-type stirrer, and 33 g of oleic acid was mixed while stirring and mixing. Stir for 1 hour. Then, 167 g of montanic acid ester wax “Hoechst-Wax E” (manufactured by Hoechst) was mixed with the mixture, and the liquid temperature was 90 to 95%.
C. and stirred for about 2 hours at this temperature.
When the temperature was lowered to 30 ° C and filtered with a cotton cloth, component (A)
A slightly yellow emulsion (A-1) containing 6.7% was obtained, which had excellent stability and did not separate at all after standing for 3 months.

(A-2) Except that Hoechst-wax E in (A-1) was changed to Hoechst wax KPE (trade name, manufactured by Hoechst), the same treatment as above was carried out. As a result, the component (A) contained 16.7%. A slightly yellow emulsion (A-2) was obtained, which was also excellent in stability and did not separate at all even after standing for 3 months.

<Preparation of (B) Component Emulsion> (B-1) 300 g of a silicone resin having (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ = 0.85 was added to the following formula.

Embedded image Dissolved in 300 g of cyclic dimethylpolysiloxane represented by
To this were added 8.7 g of polyoxyethylene sorbitan monolaurate (mol added EO: 20 mol, HLB = 16.7), 20.5 g of sorbitan monolaurate (HLB = 8.6), and 20.9 g of sodium dialkylsulfosuccinate (70% aqueous solution), The mixture was stirred at a high speed for about 5 minutes with a homomixer.

Then, while stirring, 320 g of deionized water was gradually added dropwise thereto, and the phase was inverted. When the viscosity was increased, the stirring was stopped. The stirring speed was increased to 3,000 rpm, and the mixture was stirred at high speed for about 15 minutes. The mixture was diluted with deionized water, diluted with 30 g of polyoxyethylene octylphenyl ether (mol of EO added: 9 mol, HLB = 13.6), and stirred at low speed to obtain a white emulsion (B) containing 30% of the component (B). -1) was obtained, but it was excellent in stability, and no separation was observed even after standing for 3 months.

(B-2) Same as (B-1) except that the silicone resin used in (B-1) was changed to (CH ₃ ) SiO _1/2 unit / SiO ₂ unit = 0.65. After processing it,
(B) White emulsion containing 30% of component (B-2)
This was excellent in stability and no separation was observed even after standing for 3 months.

<Preparation of Component (C) Emulsion> (C-1)

Embedded image 50 g of a 10% aqueous solution of lauryl sulfuric acid is slowly dropped into 350 g of the cyclic dimethylpolysiloxane shown in the above while stirring at a low speed with a homomixer, and the phase is inverted. When the viscosity increases, the stirring speed is increased to 3,000 rpm and the stirring speed is increased for about 15 minutes. After high-speed stirring, the remaining lauryl sulfate aqueous solution and 600 g of deionized water were added for dilution. Then, this was subjected to secondary emulsification using a high-pressure homogenizer at a pressure of 300 kg / cm ² , and then left at 70 ° C. for 5 hours to carry out a polymerization reaction, and cooled to about 15 ° C.
When about 5 g of a 10% aqueous sodium carbonate solution was added for neutralization, a white emulsion containing 30% of a highly polymerized organopolysiloxane having an average degree of polymerization of about 3,500 was obtained.
This was excellent in stability, and no separation was observed even after standing for 3 months.

(C-2) Amine equivalent 6,500, viscosity 60 cS
Is the following equation

Embedded image Are weighed in a polyethylene container and mixed with high-speed stirring for about 5 minutes with a homomixer for 20 minutes. The resulting mixture was mixed with 200 g of the amino group-containing organopolysiloxane represented by the above formula and 30 g of polyoxyethylene tridecyl ether (mol of EO added: 10 mol, HLB = 13.6). . Then, 770 g of deionized water was gradually added dropwise thereto while stirring at a low speed, and the phase was inverted.
After increasing the stirring speed to 3,000 rpm and stirring at a high speed for about 15 minutes, the remaining water was added for dilution, and the white emulsion (C-2) containing 20% of the above-mentioned amino group-containing organopolysiloxane was obtained, This product had excellent stability, and no separation was observed even after standing for 3 months.

(C-3) The amino group-containing organopolysiloxane used in (C-2) has an amine equivalent of 1,900, a viscosity of 750 cS and the following formula:

Embedded image Except as indicated by the above, the same treatment as in the above (C-2) gave a white emulsion (C-3) containing 20% of this amino group-containing polysiloxane, which was stable. The properties were excellent, and no separation was observed even after being left for 3 months.

Example 1 375 g of emulsion (A-1), emulsion (B-1)
543 g, 43 g of emulsion (C-1) and 39 g of polyoxyethylene octyl phenyl ether (mol of EO added: 9 mol, HLB = 13.6) were weighed into a container, and mixed by low-speed stirring with a homomixer for about 20 minutes. A slightly yellow emulsion composition was obtained, which had excellent stability, and no separation was observed even after standing for 3 months.
Then, this was diluted three times with deionized water and subjected to a peeling test and observation of a cell state. As a result, the results shown in Table 1 described later were obtained.

Example 2 375 g of emulsion (A-1), emulsion (B-1)
500 g, 86 g of the emulsion (C-1), and 39 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 1 described later were obtained.

Example 3 Emulsion (A-1) 375 g, Emulsion (B-2)
543 g, 43 g of emulsion (C-1), and 39 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were mixed and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 1 described later were obtained.

Example 4 Emulsion (A-1) 268 g, Emulsion (B-2)
543 g, 150 g of emulsion (C-1), and 39 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 1 described later were obtained.

Example 5 Emulsion (A-2) 375 g, Emulsion (B-1)
543 g, 43 g of emulsion (C-1), and 39 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were mixed and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 1 described later were obtained.

Comparative Example 1 Emulsion (A-1) 168 g, Emulsion (B-1)
543 g, 250 g of emulsion (C-1), and 39 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were mixed and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 1 described below were obtained.
This product was excellent in releasability due to the large amount of component (C), but had a large nonuniform cell diameter.

Comparative Example 2 Emulsion (A-1) 411.5 g, Emulsion (B-
1) 543 g, 6.5 g of emulsion (C-1), and 39 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were mixed and treated in the same manner as in Example 1 to obtain a slightly yellow emulsion composition. A product was obtained, which had excellent stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 1 below were obtained.
Although the average cell diameter was small due to the small amount of the component (C), the appearance of the urethane molded article was good.
The releasability was poor.

[0044]

[Table 1]

Example 6 Emulsion (A-1) 359 g, Emulsion (B-1)
478 g, 120 g of emulsion (C-2), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Example 7 Emulsion (A-1) 359 g, Emulsion (B-1)
398 g, emulsion (C-2) 200 g, and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Example 8 Emulsion (A-1) 359 g, Emulsion (B-1)
478 g, 120 g of emulsion (C-3), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Example 9 Emulsion (A-1) 359 g, Emulsion (B-2)
478 g, 120 g of emulsion (C-2), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Example 10 Emulsion (A-1) 359 g, Emulsion (B-2)
538 g, 60 g of emulsion (C-2), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were mixed and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Example 11 359 g of emulsion (A-2), emulsion (B-1)
478 g, 120 g of emulsion (C-2), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Example 12 Emulsion (A-2) 359 g, Emulsion (B-1)
478 g, 120 g of emulsion (C-3), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.

Comparative Example 3 Emulsion (A-1) 359 g, Emulsion (B-1)
298 g, 300 g of emulsion (C-2), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peel test and a cell state of the diluted water were observed. As a result, the results shown in Table 2 described below were obtained.
This one had excellent releasability due to the large amount of the component (C), and had a large nonuniform cell diameter.

Comparative Example 4 Emulsion (A-1) 359 g, Emulsion (B-1)
588 g, 10 g of the emulsion (C-2), and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were mixed and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. However, this was excellent in stability, and no separation was observed even after standing for 3 months. Then, this was diluted three times with deionized water, and a peeling test and a cell state of the diluted water were observed. As a result, the results shown in the following Table 2 were obtained. , The mold releasability was poor.

[0054]

[Table 2]

Example 13 Emulsion (A-1) 359 g, Emulsion (B-1)
478 g, emulsion (C-1) 60 g, emulsion (C
-2) 60 g and 43 g of the same polyoxyethylene octyl phenyl ether used in Example 1 were blended and treated in the same manner as in Example 1 to obtain a pale yellow emulsion composition. Has excellent stability and 3
There was no separation after standing for months. Then, this was diluted three times with deionized water, and a mold release test and a cell state were observed. This revealed that the C component was a combination of a high-hardness organopolysiloxane and an amino-containing organopolysiloxane. Since the mixing ratio of the A, B and C components is A / B / C = 26/61/13, the peeling force is also 20%.
It was excellent at 0 g / 2.5 cm, and the obtained molded article had a good appearance and an average cell diameter of 100 μm.

[0056]

The present invention relates to a release agent composition, which comprises, as described above, (A) a wax,
(B) the silicone resin described in detail above, and (C) the silicone resin described in detail above.
The high polymerization degree organopolysiloxane described above and / or
The amino group-containing organopolysiloxane described in detail above ,
(D) An emulsifier is emulsified and dispersed in water at a specific ratio. When this is applied to a mold at the time of producing a polyurethane molded product, the molded product can be released from the mold better.
This has the advantage that a polyurethane foam molded article having a good cell state can be obtained because it does not hinder polyurethane foaming.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Satoshi Kuwata 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-61-27141 JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B29C 33/64 C08L 83/04-83/08

Claims (2)

(57) [Claims] 1. A (A) a wax 1-15 wt%, (B) formula R ¹ ₃ SiO _1/2 units, SiO ₂ units, R ¹ ₂ SiO units, R ¹ SiO _3/2 units (where R ¹ in consists unit selected from monovalent hydrocarbon groups) of 1 to 6 carbon atoms, the total amount of R ¹ ₃ SiO _1/2 units and SiO ₂ units of these all the structural units is 80 mol% or more, the R ¹ ₃ SiO _1/2 units / SiO ₂ molar ratio units organic solvent-soluble silicone resins 10-30% by weight in the range of 0.5 to 1.5, a high polymerization represented by (C) the following formula (formula 1) Degree organopolysiloxane and / or formula R ⁴ _a R ⁵ _b R ⁶ _c SiO _{(4-abc) / 2} [where R ⁴ is -R ⁷ (NR ⁸ CH ₂ CH ₂ ) _n NR ⁹ R ¹⁰ (R ⁷ Is a divalent hydrocarbon group having 1 to 4 carbon atoms , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms , and n is an amino represented by 0 ≦ n ≦ 4) alkyl group, R ⁵ is a monovalent hydrocarbon substituent was or unsubstituted C1-8 Containing group, R ⁶ is a monovalent hydrocarbon group R ¹¹ with water acid groups or alkoxy groups represented 1-6 hydrogen atoms or carbon atoms in OR ^11, a, b, c is 0.0001 ≦ a ≦ 1, 1.8 ≦ 1.8 <a + b + c <2.3] where b ≦ 2.2, 0 ≦ c ≦ 0.1, an amine equivalent is 500-100,000 (g / mol), and an amino group-containing organopolysiloxane having a viscosity at 25 ° C. of 10-100,000 cS. 0.5 to 10% by weight, [Formula 1] (Where R ² is the same or different unsubstituted C 1-8)
Or a substituted monovalent hydrocarbon group, R ³ is a hydrogen atom, methyl
Group, ethyl group, vinyl group, phenyl group, hydroxyl group, alcohol
An atom or group selected from a xy group, m is 2,000 to 20,0
00) (D) 1 kind or emulsifier 0.5 to 30 wt% on the two or more kinds selected from non-ionic emulsifiers and ionic emulsifiers, made of (E) water balance, the (A) component (B) Wherein the ratio of the total amount of (C) and (C) is [(A) + (B)] / (C) = 99/1 to 75/25. 2. The release agent composition according to claim 1, which is a release agent for producing a polyurethane molded article.