JPS5932514B2 - mold release agent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mold release agent composition, more specifically, a mold release agent suitable for molding a molded product of a synthetic resin or a polymeric substance such as rubber, and particularly for molding a urethane molded product. Regarding the composition.

Conventionally, when molding a molded product from acrylic resin, epoxy resin, urethane resin, vinyl chloride resin, vinyl acetate resin, synthetic rubber, etc., a release agent was used to make it easier to release the mold from the mold. Applying an agent is performed.

However, since it is particularly difficult to release materials that exhibit strong adhesive properties such as urethane resins and epoxy resins from molds, various mold release agents have been proposed for urethane resins, which have been in increasing demand in recent years. For example, polyethylene wax is known (see Japanese Patent Publication No. 56-5844), but this wax has poor mold release properties, and especially when molding is performed continuously, the mold release agent may not be present in the mold. In addition, there are disadvantages such as deposits of mold release agent powder, scattering of the mold release agent powder, contaminating the surrounding area, and loss of gloss of the resulting molded product. mold release agent (Pelky Patent No. 814909), α-
A silicone mold release agent (Japanese Patent Publication No. 52-3
No. 2780) has also been proposed, but all of these mold release agents have heavy mold release properties and do not wet the mold uniformly, so some of the urethane resin remains on the mold, making it difficult to release. It has the disadvantage of On the other hand, silicone mold release agents have a "sticky feeling" and a "repellent phenomenon" of paint due to transfer to the molded object, but in order to improve these problems, a mixture of perfluoroalkyl phosphate and silicone is used. (Japanese Patent Publication Nos. 53-23270 and 53-23271) are known, but these do not have sufficiently satisfactory release properties and cannot withstand repeated use (
A composition comprising perfluoroalkyl phosphate and silicone varnish has been proposed to solve this problem and provide excellent three-dimensional molding (Japanese Patent Application Laid-Open No. 133490/1983). This product has the drawbacks of being difficult to dissolve in chlorinated solvents and being difficult to peel off.The present invention aims to provide a new mold release agent composition that eliminates the drawbacks of conventional mold release agents as described above. (a) R3SlO% unit, R2
Consisting of SlO units and SiO2 units (wherein R represents the same or different groups or atoms selected from hydrogen atoms, methyl groups, vinyl groups, and phenyl groups), provided that at least 50 mol% of R is a methyl group. ), R
3SlO%/SiO2 is 0.4 to 2.0 (molar ratio),
10 to 90% by weight of an organic solvent-soluble silicone resin in which R2SlO/SiO2 is O to 1.0 (molar ratio), and (iii) a general formula (wherein Rf is a straight chain having 4 to 15 carbon atoms or Branched perfluoroalkyl group, R5 has 1 to 1 carbon atoms
The above-mentioned polyfluoroalkyl group-containing polymer according to the present invention is obtained by polymerizing or copolymerizing unsaturated esters represented by 10 alkylene groups, where the end is a hydrogen atom or a methyl group. The composition consisting of components (A) to (C) has the following properties: 1. It has good wettability and can be applied uniformly to the mold; 2. It has light peeling and can be applied 3 times.
4) The surface of the molded product after molding is clean and glossy, 5 urethane resin residue does not accumulate on the mold, 6 there is little contamination around the molding machine, etc. Also,
Since the composition has excellent mold release properties, it can be used as a mold release agent in the molding of urethane resins, polymer resins such as epoxy resins and acrylic resins, natural rubber, synthetic rubber, etc., and can also be used in paints, latex, etc. It can also be applied to anti-blocking agents for leather coated with synthetic resins, etc.〇The present invention will be explained in detail below.〇In the present invention, (
B) The silicone resin as a component shows the action as a film forming agent, and this resin has R3SIO% units (M units), R2SiO units (D units) and SlO2 units (
In the present invention, the molar ratio of M units to Q units (M/Q) is in the range of 0.4 to 2.0, preferably 0.6 to 1.5. , it is essential that the molar ratio (D/Q) between D units and Q units is in the range of O to 1.0. R in the formula is a hydrogen atom, a methyl group, a vinyl group, or Represents the same or different groups or atoms selected from phenyl groups;
0 Such silicone resins can be obtained by various conventionally known methods, such as trialkylmonochlorosilane, hexamethyldisiloxane, or If so, dichlorosilane (R2SlCl2) is used in combination, and benzene, toluene, xylene, etc. Next, the amino group-containing organopolysiloxane as an ingredient used in the present invention is produced as a material soluble in organic solvents.
, or H2NCH2CH2N{M2CH2CH2 The molecular structure may be either linear or branched as long as it has at least one element such as is 10~
A value in the range of 1000 cS is desirable.

There is no particular restriction on the groups other than the amino group bonded to the Si atom in this siloxane, and the same groups as those exemplified above for R can be mentioned, and such amino group-containing organopolysiloxane Examples include the compounds shown below. however,
In the following description, Me, Et and Ph represent a methyl group, an ethyl group and a phenyl group, respectively.

Furthermore, the polyfluoroalkyl group-containing polymer used in the present invention as component (iii) has the general formula (wherein Rf is a linear or branched perfluoroalkyl group having 4 to 15 carbon atoms). group, w is an alkylene group having 1 to 10 carbon atoms, w is a hydrogen atom or a methyl group). In the invention, it is preferable to use a polymer having excellent compatibility or dispersibility with silicone.

Such a polyfluoroalkyl group-containing polymer specifically has 3 to 20 carbon atoms (preferably 4 to 20 carbon atoms), such as
15) A polymer obtained from unsaturated esters represented by (meth)acrylates containing a perfluoroalkyl group, or one type of compound that does not contain a fluoroalkyl group and can be polymerized with such unsaturated esters. Alternatively, copolymers with two or more types can be mentioned. Examples of compounds that do not contain a fluoroalkyl group that can be polymerized with these unsaturated esters include ethylene, vinyl acetate, vinyl chloride, acrylonitrile, styrene, (meth) Acrylic acid or its esters, maleic anhydride, etc. can be mentioned, and the polymerization can be carried out according to conventionally known methods, for example, the method described in Japanese Patent Publication No. 37-18627.

The polyfluoroalkyl group-containing polymer corresponding to component (iii) is used as a water- and oil-repellent agent for fibers or various surface water- and oil-repellent treatment agents, and commercially available products include Asahi Glass ( Examples include AG-655 manufactured by Sumitomo 3M Co., Ltd. and Scotch Guard FC-905 manufactured by Sumitomo 3M Limited.

This component acts to uniformly wet the surface of the mold with the component (a), and by incorporating this component, peeling becomes easier and it becomes possible to remove the mold several times.

The composition according to the present invention consists of the three components described above, and the proportion of each component used is (a) component...10 to 90
Weight% (preferably 75-90%) Ingredients...0-8
0% by weight (preferably 1-20%) l (-→components...
0.1 to 10% by weight (preferably 1 to 5% by weight) 1 This is because a) If the proportion of the component used is less than 10% by weight of the total, the desired mold release performance will deteriorate. On the other hand, if it exceeds 90% by weight, it becomes difficult to uniformly wet the surface of the mold, and peeling becomes difficult, making it impossible to measure the number of times.

If the (mouth) component is 80% by weight or more, peeling becomes difficult and the cells become rough, making it difficult to use. Furthermore, as the ratio of the ('→ component used) increases, the peeling becomes easier, but conversely, when it exceeds 10% by weight, it becomes heavier.

The composition according to the present invention is prepared by uniformly mixing predetermined amounts of the above-mentioned (a) to o→ components, which usually include:
It is used suspended or dissolved in aromatic hydrocarbon solvents or chlorinated hydrocarbon solvents*, but it is also emulsified and
/It is also possible to use it in the form of a W-type emulsion./The composition of the present invention may optionally contain dimethylpolysiloxane, methylphenylpolysiloxane, and the above-mentioned materials.
Amino group-containing polysiloxanes other than the ingredients, diorganopolysiloxanes such as methylpropylorganopolysiloxane, waxes such as polyethylene wax, carnauba wax, and beeswax, fatty acids such as stearic acid and behenic acid, or their esters, Fillers such as silica filler may be added and blended within a range that does not impair the object of the present invention.

The mold release agent obtained in this way can be applied to the mold by any means, such as brushing or spraying, and then the solvent can be removed by drying, thereby forming a mold release film with excellent properties as described above. can be obtained.

Next, Examples of the present invention will be given, and all "parts" in each example indicate parts by weight.

Example First, mold release agents A-J having the following composition were prepared.

However, mold release agents A-F are products of the present invention, and G-J are control products.

Mold release agent A; (1) Me3SiOH. :5Si02, Me
40 parts of silicone resin with a ratio (M:Q) of 3SiOH and SlO2 of 1:0.5, (3) CH2=CHC
OO(CH2)3(CF2)6CF(CF3)273w
Copolymer 4 consisting of t%, 25 wt% ethyl acrylate and 2% diacetone acrylamide.

10 parts (1) Me3SiOH2O mol%, Me-HSiO4
20 parts of a silicone resin consisting of O mol%, SiO24 mol%, 50 wt%, 5 parts of a copolymer consisting of styrene 25 wt%, methyl methacrylate 25 wt%, (
4) Viscosity 10,000 cS (25°C offshore dimethyl polysica xane 65 parts mold release agent C; (1) Me3SiOH (consisting of 5Si02, Me3
20 parts of silicone resin with a ratio of SiOK to SiO2 (M:Q) of 1:1, (3) 5 parts of the same (3) component used in mold release agent A, ? ', (5) 10 parts of polyethylene wax (melting point 60°C), mold release agent D; (1) consisting of Me3SiOh and SiO2,
10 parts of silicone resin with a ratio of Me3SiOK to SiO2 (M:Q) of 1:1, (3) Same as that used in mold release agent B (3) 0.1 part of component mold release agent E; (1 ) Same as that used in mold release agent D (1) 10 parts of ingredients, (2) Same as that used in mold release agent D (
2) 8 parts of component β, same as that used in (3) mold release agent D (3) 2 parts of component, mold release agent F; (1) Me3SiOH and (CH2=CH)Me2Si
Composed of OK and SiO2, each component is Me3SiOh
4O mol%, (CH2=CH)Me2SiOKlO mol%, SiO25O mol%, i.e. R3SiOK and Sl
10 parts of silicone resin with an O2 ratio of 1:1, (2
) Same as that used in mold release agent D (2) component 88
Part, (3) Same as that used in mold release agent D (3)
2 parts of component, mold release agent G; (1) Same as that used in mold release agent D. (1) 10 parts of component, (2) Same as that used in mold release agent D (
2) Separable mold agent H; trade name KS-707 (manufactured by Shin-Etsu Chemical Co., Ltd., dimethyl silicone mold release agent) mold release agent I; commercially available product (consisting of dimethylpolysiloxane and wax)
Commercially available mold release agent (wax type) Mold release agent K: (1) Me3SiOH, PhMe2SiO% and S
Consisting of iO2, each component is Me3SiOK4O mol%,
PhMe2SiOKlO mol%, SiO25O mol%,
That is, 10 parts of silicone resin with a ratio of R3SiOH and SiO2 of 1:1, (2) 85 parts of the same component as used in mold release agent D, (3) same as that used in mold release agent D. (3) The mold release agent A-K consisting of 5 parts of ingredients and the above composition was examined for peeling test, count test, and appearance of the molded product as described below, and the results are shown in the table.

In addition, mold release agents A-F and K are dissolved in methylene chloride.
It was used as a 0% solution.

Claims (1)

[Claims] 1 (a) R_3SiO_1_/_2 units, R_2Si
Consisting of O units and SiO_2 units (in the formula, R represents the same or different groups or atoms selected from a hydrogen atom, a methyl group, a vinyl group, and a phenyl group. However, at least 50 mol% of R is a methyl group)
, R_3SiO_1_/_2/SiO_2 is 0.4 to 2
．． 0 (molar ratio), R_2SiO/SiO_2 is 0 to 1
．． 10 to 90% by weight of an organic solvent-soluble silicone resin having a molar ratio of 0 (molar ratio), (b) 0 to 80% by weight of an amino group-containing organopolysiloxane, and (c) the general formula R_fR′OCOCR″=CH_2 (in the formula, R_f is a linear or branched perfluoroalkyl group having 4 to 15 carbon atoms, and R' is 1 carbon atom.
Polyfluoroalkyl group-containing polymer obtained by polymerizing or copolymerizing unsaturated esters represented by ~10 alkylene groups, R'' is a hydrogen atom or a methyl group)
．． A mold release agent composition comprising 1 to 10% by weight of the following as a main component.