JPS60190309A - Releasing agent - Google Patents

Abstract

PURPOSE:To obtain a releasing agent excellent in releasing property and solubility and having good storage stability for polyurethane and various resins and rubbers, containing a specific phosphonic acid monoester (salt), a low-melting wax and an oil. CONSTITUTION:A phosphonic acid monoester (salt) of the formula (where Rf is a 1-20C polyfluoroalkyl, R' is a divalent organic group, and R is a hydrocarbon) is mixed a wax or oil (preferably silicone oil) of a melting point of 100 deg.C or less in a proportion of 1: 0.2-5wt. ratio preferably to obtain a releasing agent. The compound of the formula is obtained from reaction of a compound of the formula Rf-R'-X (where X is a halogen) (e.g., C6F13O2H4I, etc.) with a compound of the formula P(OR)3 [e.g., P(OCH3)3, etc.].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mold release agent. More specifically, the present invention relates to a mold release agent that has excellent mold release properties and solubility.

A phosphonic acid or an acid salt thereof represented by the general formula (where Rf is a, ~0□. polyfluoroalkyl group, and R' is a divalent organic group) and a wax having a melting point of 100°C or less, or 1 liter containing oil as an essential ingredient
The llt type agent was previously proposed by the applicant (
Japanese Unexamined Patent Publication No. 180,597/1982, Patent Application No. 17/1983
7.330 and 58-41891).

Although such mold release agents sufficiently exhibit the desired effect in terms of mold release properties, they have the following problems because phosphonic acid or its acid salt has low solubility in solvents with low polarity. There is.

(a) Since it must be used as a dispersion system, it tends to cause uneven coating when applied to molds, etc. (b) 1.
In order to prevent the deterioration of mold releasability due to such causes, it is necessary to use more lids for one application, which leads to high costs. The present inventors have found that this can be effectively achieved by monoesterifying the phosphonic acid represented by the formula [1] or its acid salt with a hydrocarbon group such as an alkyl group, an aryl group, or an aralkyl group. Served.

Accordingly, the present invention relates to a mold release agent, which is a phosphonic acid monomer represented by the general formula (wherein Rf and R' are as defined above and R is a hydrocarbon group). It contains an ester or a salt thereof and a wax or oil having a melting point of 100°C or less.

The phosphonic acid monoester or its salt represented by the above general formula [II] is synthesized through the following steps.

(1) Rf-R'-X+ P(OR), (X:
Example of Rf-R'-X used (halogen atom): 04PI3'2H4% 0BFT702"4"11
17210384 -, 0,2F250H201, preferred Ly < l″i0!IP+702H4i0!IP+
702H4 engineering use: (8) If desired, neutralize with an appropriate base to form a salt.

Salt formation can be achieved using, for example, ammonium hydroxide, ammonium hydroxide, zinc sulfate, zinc acetate, zinc oxide, triethylamine, triethanolamine, (2-hydroxyethyl)amine, etc., usually at pH. Titrate with the above-mentioned salt-forming reactant while checking the equidispersion point, and titrate with the acidic 1
- Trivalent metal salt, amine salt or ammonium salt.

The phosphonic acid monoester (salt) synthesized in this way contains a wax or oil having a melting point of 100°C or less in a weight ratio of about 0.05 to 10, preferably about 0.2 to 5. A mold release agent is prepared by blending. Examples of waxes or oils with a melting point of 100°C or lower include vegetable wax, animal wax, petroleum wax, silicone oil,
Fluorine oil, mineral oil, vegetable oil, animal oil, synthetic oil, phosphate ester oil, etc. are used, and silicone oil represented by dimethylosiloxane is particularly preferred. This is done by dissolving the salt and wax or oil in an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, polyhydric alcohols such as methyl cellosolve, ethyl cellosolve, methyl calpitol, and ethyl calpitol. At least one type of halogenated hydrocarbons such as derivatives, carbon tetrachloride, methylene chloride, ethylene chloride, trichlorethylene, perchlorethylene, trichloroethane, trichlorofluoromethane, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. is used. , or these organic solvents may be used in combination with water. The most preferred solvent system is a mixed solvent of isopropanol and trichlorotrifluoroethane (Freon 113).

Even if phosphonic acid monoester or its salt is dissolved in these organic solvent systems at a concentration of about 0.1% by weight or less, it will not be effective when applied to the object to be released. Demonstrates mold release performance. That is, the mold release agent according to the present invention provides excellent mold release that could not be easily achieved even with a mold release agent prepared to account for m% of phosphonic acid monoester, which exhibits extremely good organic solvent solubility. It is easy to obtain sex. Furthermore, because of its good solubility, the mold release agent of the present invention easily forms a homogeneous system, so it does not form precipitates unlike conventional mold release agents, and has good storage stability. be.

The mold release agent can be applied to the mold by any commonly used method, such as dipping, spraying, brushing, aerosol spraying, or coating with an impregnated cloth. Examples of molding materials molded using a mold coated with a release agent include resins such as polyurethane, polycarbonate, epoxy resin, phenol resin, polyimide resin, and vinyl chloride resin, natural rubber, chloroglene rubber, and fluorine rubber. Rubbers such as

Next, the present invention will be explained with reference to examples.

EXAMPLE 10 parts by weight of phosphonic acid monoisopropyl ester are dissolved in 10 to 20 parts by weight of Impropatol, and 100 to 300 parts by weight of a water-itubrobanol (10:1) mixed solvent are added thereto while stirring well.

Add 10~ to the generated colloidal solution while stirring well.
(50% hydroxide) Add IJum aqueous solution dropwise and adjust the pH to 2.
~ Neutralize from 3 to 7. This neutralization turns the colloidal solution into a true solution. To this, 6 parts by weight of zinc sulfate, 7
An aqueous solution of 50 to 100 parts by weight of water salt completely dissolved in water was added dropwise with thorough stirring to make the pH acidic again to 3 to 4, and the resulting precipitate was extracted with trichlorotrifluoroethane.

Preparation of mold release agent and evaluation of i-type property Phosphonic acid monoisopropyl ester acid zinc salt synthesized as above and silicone oil (Shin-Etsu Chemical Kl' 96-350 as or X-62-8
53) was dissolved in a mixed solvent of 7 Leon 113-isopropatol to prepare a mold release agent.

This mold release agent is applied to the molding surface of a steel split mold in which bellows-shaped grooves are carved, and two of these split molds are used to form a cylindrical body having a bellows-shaped outer peripheral surface. After forming, the mold is preheated to 70-80°C.

Separately, add 30 parts by weight of polyurethane prepolymer (100 parts by weight of aliphatic polyester having a molecular weight of about 10,000 and 30 parts by weight of diphenylmethane diisocyanate to 130°C.
(prepared by mixing at 120°C, reacting, and then maintaining at 120°C) 6
6 g and 1 g of a blowing agent (prepared from 100 parts by weight of distilled water, 50 parts by weight of a silicone foam stabilizer and 3 parts by weight of a catalyst) were quickly mixed and stirred, and this was poured into the mold,
Close the lid and secure with a clamp. This was heated to 100°C for 10
After heating for a minute, the lid was removed and the mold was forcibly separated into separate molds to release the molded product, and the following five items were observed. This operation was counted as one shot, and was repeated up to 10 shots (up to 3 shots for A8 and 12 in the table below).

(Mold releasability evaluation 1ifli) A: The molded product can be easily removed from the mold. B: The molded product has cracks and missing parts, and these remain attached to the mold (presence or absence of scum) Molding of the mold Remove debris from the molding that adheres to parts other than the surface (mainly the gap between the split molds) with a diameter 51
Compressed air spouted from the nozzle of 1III (2~3~)
A: There is no residue or it is easy to remove. B: The residue can be removed, but there are some areas that are difficult to remove with just compressed air. 0: There are areas that cannot be removed without rubbing by hand. D: There are quite a few areas that cannot be removed without rubbing by hand.It cannot be removed even by hand rubbing (stains on the molded surface).A: Mirror-like after 5 or more Nijiyots. 8: Mirror-like after 4 Nijoyotes. A: There is a slight stiffness after the 1st time of a certain O.D. It gradually becomes white from the 1st time of a rainbow yotting.yh Nijiat fBJ It becomes white from the 1st time of a rainbow yotting (texture of the surface of the molded product) A: Dry without sticky feeling fC feeling B: There is no sticky feeling, but it feels damp a: It feels a little sticky D: It feels quite sticky m + It feels quite sticky and damp (line of sight of the surface of the molded product) A ; Fairly smooth and glossy B: Smooth but not glossy 0: Slightly uneven D: Fairly uneven E: Fairly uneven with defects such as cracks Composition of the mold release agent and its release properties The evaluation results are shown in the table below. In addition, A1-7 are Examples using phosphonic acid monoisoglobil ester acidic zinc salt and silicone oil, A8-11 are comparative examples using the corresponding phosphonic acid acid zinc salt and silicone oil, and A12 ~1
Sample No. 3 is a comparative example in which only silicone oil was used without using phosphonic acid (monoester) salt, and A14 is a comparative example in which only acidic zinc salt of phosphonic acid was used without using silicone oil.

Claims (1)

[Claims] 1. Phosphone represented by the general formula (where Rf is a polyfluoroalkyl group of O1 to 020, R/ is a divalent organic group, and R is a hydrocarbon group) A mold release agent containing an acid monoester or a salt thereof and a wax or oil having a melting point of 100°C or less. 2. The mold release agent according to claim 1, wherein the oil is silicone oil.