JPH03234509A - Mold release agent - Google Patents

Abstract

PURPOSE:To obtain a mold release agent having excellent mold release characteristics even in the case of the molding of a thermosetting resin which has high adhesion properties by dissolving or dispersing a specific fluorine- containing organosilicon compound into an aqueous medium. CONSTITUTION:A fluorine-containing organosilicon compound represented by the formula I is dissolved or dispersed in an Aggeus medium. In the formula I' Rf represents a fluoroalkyl group having 4 to 20 carbon atoms, R' represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R<2> represents a hydrogen atom or the same monovalent hydrocarbon group as R<1>' A and B each represents a bivalent organic group, m represents an integer of 1 to 3, x represents an integer of 2 or 3, and y represents an integer of 1 to 50. According to this formula, a mold release agent having excellent mold release characteristics can be obtained for the molding of a high molecular material, such as a synthetic resin and rubber, cement and ceramic and, furthermore, even for the molding of thermosetting resin having high adhesion properties such as a urethane resin, an epoxy resin and a phenolic resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to mold release agents, particularly for purchasing polymers such as synthetic resins and rubber, and for molding cement and ceramics, as well as urethane resins, epoxy resins, and phenol resins. The present invention relates to a mold release agent that exhibits excellent mold release properties when molding thermosetting resins with strong adhesive properties such as resins.

[Prior Art] Conventionally, natural or synthetic compounds such as silicone oil, mineral oil, paraffin wax, fatty acid derivatives, and glycols are used as mold release agents when molding polymer products, cement, ceramics, etc. have been put into practical use, but among these, silicone oil is widely used because of its excellent heat resistance and mold release properties.

However, when used for molding resins with strong adhesive properties such as urethane resins and epoxy resins, it is necessary to improve the strength of the mold release agent film, so fine powder of silicon oxide is added to it. Alternatively, silicone resin has also been added, but in this case, the release agent travels into the molded object, staining the molded object and causing mold stains, making this use difficult. However, the disadvantage was that the cost was also high.

Therefore, attempts have been made to use a perfluoroalkyl group-containing oil that has a low surface energy and is water and oil repellent for this mold release agent. Those using a mixture of containing phosphoric acid ester or its salt and silicone oil (see Japanese Patent Publication No. 53-23270 and Japanese Patent Publication No. 53-23271), phosphoric acid ester containing a perfluoroalkyl group having 4 to 20 carbon atoms, or Those using a mixture of the salt and silicone oil (see Japanese Patent Publication No. 57-48035), those using a mixture of perfluoroalkyl group-containing polyether and silicone oil (see Japanese Patent Publication No. 59-32513) , those using a ladder polymer of perfluoroalkyl group-containing silane or siloxane and organosilsesquioxane (see JP-A-1-157808), those using perfluoroalkyl group-containing phosphonic acid or its salt ( There have been many proposals regarding this perfluoroalkyl group-containing silane or siloxane (see JP-A-58-172242 to JP-A-172246).
Compounds in which silicon is bonded to perfluoroalkyl group-containing polyethers are also known (Japanese Patent Application Laid-Open No. 1-1578).
(See Publication No. 08).

[Problems to be Solved by the Invention] However, products containing perfluoroalkyl group-containing phosphoric acid esters or phosphonic acids have reactive functional groups, so that molded objects may not have reactive groups such as urethane foam. When molding a resin with a perfluoroalkyl group, a part of the resin reacts on the surface of the resin, resulting in a roughened surface of the molded product. A ladder polymer mixture of an alkyl group-containing silane or a siloxane and an organosilsesquioxane dissolved or dispersed in water lacks stability and cannot be stored for a long period of time. The disadvantage is that it is difficult to do.

[Means for Solving the Problems] The present invention relates to a mold release agent that can solve these disadvantages and drawbacks, and is represented by the general formula (where R1 is a fluoroalkyl group having 4 to 20 carbon atoms, R' has 1 or more carbon atoms
1G monovalent hydrocarbon group, R2 is a hydrogen atom or the same monovalent hydrocarbon group as R1, A and B are divalent organic groups, m is 1
It is characterized by being formed by dissolving or dispersing a fluorine-containing organosilicon compound represented by an integer of 1 to 3, X being an integer of 2 or 3, and y being an integer of 1 to 50 in an aqueous medium.

In other words, the present inventors have achieved excellent results in molding polymeric substances such as synthetic resins and rubber, cement, and ceramics, as well as in molding thermosetting resins with strong adhesive properties such as urethane resins, epoxy resins, and phenolic resins. As a result of various studies to develop a mold release agent that exhibits good mold release properties, we found that a fluorine-containing organosilicon compound represented by the above general formula (1) dissolved or dispersed in an aqueous medium was used as a mold release agent. When used, this fluorine-containing organosilicon compound has excellent mold releasability because it is a combination of a fluoroalkyl group and a polyether with a siloxane bond, and even though it is water-based, it can be easily molded into a mold. The wettability of the coating is very good, and the surface of the mold can be evenly wetted, so this mold can be used repeatedly when molding rubber, plastic, etc. at high temperatures (vulcanization), and it has excellent release properties. It shows the number of molds, and even when molding resin with strong adhesive properties, the mold release property is good, so gas from the molded product does not remain in the mold, so it is possible to mold this type of resin, which is becoming more complex and large. F in type
# It was discovered that it can be used for dense casting, and because it is water-based, it is safe, hygienic, and easy to handle, and it is stable at both low and high concentrations and has excellent storage stability. The present invention was completed after confirming that the invention was true.

This will be explained in further detail below.

[Function] The mold release agent of the present invention may have a general formula in which at least one atom is substituted with an oxygen atom, but this includes the formula % formula % (2) (where n is 4 to 20 (preferably an integer of 5 to 12), represented by a formula in which at least one carbon atom in the main chain of the perfluoroalkyl group is substituted with an oxygen atom, and R, Carbon number 4-2
0 fluoroalkyl group, R1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R2 is a hydrogen atom or the same monovalent hydrocarbon group as R1, A and B are 2 organic groups, m is 1 to 3 carbon atoms, The fluorine-containing organosilicon compound, in which X is an integer of 2 or 3 and y is an integer of 1 to 50, is dissolved or dispersed in an aqueous medium.

The Rf group in the above is a fluoroalkyl group having 4 to 20 carbon atoms, which has a small number of carbon atoms in its chain (herein a
is an integer of 1 to 5, preferably 2 to 4), and a fluoroalkyl group of the formula % (4) (where p is an integer of 2 to 1O) are exemplified. However, in this, formula (2),
The one shown in (3) is preferred.

The perfluoroalkyl group represented by this formula (2) includes a nonafluorobutyl group, a tridecafluorohexyl group, a heptadecafluorooctyl group, a 7-trifluoromethylhexadecafluorooctyl group, and a 5-trifluoromethyldodecafluoro group. Specific examples of the perfluoroalkyl ether group of formula (3) include 1-trifluoromethyl-2-oxa-octafluoropentyl group, 1,4-bis(trifluoromethyl) -2,5-dioxa-undecafluorooctyl group and 1,4.7-tris(trifluoromethyl) -
A 2,5,8-trioxa-tetradecafluoroundecyl group is mentioned.

In addition, the R1 group in the above is a monovalent hydrocarbon having 1 to 10 carbon atoms, and includes alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and pentyl group, cycloalkyl groups such as cyclohexyl group, Examples include aryl groups such as phenyl group and tolyl group, alkylphenyl groups such as methylphenyl group and ethylphenyl group, but alkyl groups, particularly methyl groups are preferred.
The 82 groups mentioned above are selected from hydrogen atoms and this R1 group.

Next, the above A is considered to be a divalent organic group,
This includes a group represented by the formula % formula % (where 83 is a hydrogen atom or a methyl group, 1 is an integer of 0 or 1), as well as a group represented by the formula % formula % (where b is 0 to 3). (an integer of ) υ.

In addition, the few organic groups represented by B in the above include divalent hydrocarbon groups having 1 to 7 carbon atoms, such as alkylene groups such as methylene group, ethylene group, trimethylene group, and tetramethylene group. However, this requires -Y-
Go-, -Y-NH-(:0--Y-0-GO, -Y-
N(R')-CO- (where Y is the above-mentioned carbon number 1 to 7
A divalent hydrocarbon group represented by (R' is a hydroxyalkyl group or an alkyl group) is also exemplified.

Furthermore, the formula -(C,H2) contained in the above general formula (1)
xO) ll-++・The polyether group represented by (5) imparts hydrophilicity to the fluorine-containing organosilicon compound represented by general formula (1), making it easier to dissolve or disperse in an aqueous medium. This also has an effect on the wettability of this compound to the mold, examples of which include polyethylene glycol chains, polypropylene glycol chains, and copolymers of ethylene oxide and propylene oxide. However, this copolymer may be either a block polymer or a random polymer.

Incidentally, the group represented by Rf-A- in the fluorine-containing organosilicon compound represented by the above general formula (1) is, for example, a group represented by the formula Rr-A'-C)I-CH2 having a vinyl group at the end.
A hydrogen atom bonded to a silicon atom (=
An organohydrodiene polysiloxane or the like having a SiH bond) may be introduced into the compound represented by the general formula (1) by an addition reaction in the presence of a platinum-based catalyst, or The group represented by the formula % may also be introduced into the compound represented by the general formula (1) by an addition reaction using the platinum-based catalyst described above.

Next, as specific examples of the fluorine-containing organosilicon compound represented by the general formula (1) containing the above-mentioned Rt, R', R2, A, and B groups, the following are exemplified (Me
indicates a methyl group).

p Me Me 1J+1 The mold release agent of the present invention can be obtained by dissolving or dispersing the fluorine-containing organosilicon compound represented by the above general formula (1) in an aqueous medium. This concentration cannot be specified because it needs to vary depending on the intended use of the mold release agent, but if the purpose is only one time of mold release, it can usually be 0.1% by weight or less, and - In order to maintain mold releasability even during long-time work in applying the molding agent, the amount is preferably 0.5 to 20% by weight, preferably 1 to 10% by weight.

This mold release agent is used when molding polymeric products such as synthetic resins and rubber, cement and ceramics, and also when molding thermosetting resins with strong adhesive properties such as urethane resins, epoxy resins, and phenolic resins. Although this mold release agent is said to be useful as a mold release agent, it can be applied to the mold using conventional methods, such as immersing the mold in this mold release agent liquid or applying the mold release agent to the mold The mold release agent may be applied by spraying, brushing, or rubbing with a cloth impregnated with the release agent, and then the medium may be applied by evaporation.

The mold release agent of the present invention is made by dissolving or dispersing the fluorine-containing organosilicon compound represented by the general formula (1) in an aqueous medium as described above, and silicone oil, silicone varnish, etc. Alternatively, a surfactant or a mixture thereof may be added, thereby further improving the mold releasability.

This silicone oil may be a non-curing organopolysiloxane that is liquid or semi-solid at room temperature and has a boiling point of 100°C or higher and a melting point of 150°C or lower. It is preferable to use one having a high methyl group content, and more preferably one with a high methyl group content.

In addition, this silicone varnish is CH35iOsz2 (C
H3)2SiO, (CH3)3SfO172,5i02
Copolymers are said to have a three-dimensional structure, consisting of various combinations of structural units such as It is preferable to use one that is soluble in a solvent.

Next, the surfactant used here may be any of the usual anionic, cationic, nonionic, and amphoteric surfactants, and there is no reason to specifically limit this. Examples of the anionic surfactant include higher fatty acid alkali salts, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl phosphates, fluorine-containing carboxylic acids, fluorine-containing sulfonic acids, etc. Examples of activators include higher amine halogenates, alkylpyridium halides, and quaternary ammonium salts, and examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, Examples include sorbitan alkyl esters and sugault esters, and examples of amphoteric surfactants include secondary and tertiary amines, including betaine type and imidacilline type, and quaternary ammonium salts. It is said that those containing carboxylic acid, sulfuric acid ester, sulfonic acid, and phosphoric acid ester as anionic groups are useful.

The amount of silicone oil, silicone varnish, and surfactant to be added can be determined over a wide range, but it is preferably 500 parts by weight per 100 parts by weight of the fluorine-containing organosilicon compound represented by general formula (I). The amount is preferably within the range of 0 to 300 parts by weight, which reduces the transfer of the mold release agent to the molded product, eliminates stickiness of the molded product, and provides excellent release. Typeness is given.

However, when silicone oil or silicone varnish is added, it may be difficult for the silicone oil or silicone varnish to be dispersed in water, and in this case, the prepared mold release agent will have poor storage stability. For silicone varnish, it is generally best to add an emulsifier to form an aqueous emulsion and then add it to a fluorine-containing organosilicon compound and mix it. For silicone oil, in particular, emulsifiers such as dodecylbenzenesulfonic acid and sodium lauric sulfate are added. It is preferable to use emulsion polymerization.

[Example] Next, examples of the present invention and comparative examples will be given.
% indicates parts by weight and % by weight, viscosity is 25
The values measured at °C are shown, and the test method for mold releasability, stickiness of molded products, and residual degree of residue in the examples were determined according to the following table.

<m-type property) Mold release property is determined by applying a mold release agent once, without further application,
This process was continued until the mold releasability deteriorated.

(Stickyness of molded product) In the mold releasability test, the appearance of the molded product released from the mold for the first time was felt, and the stickiness at that time was evaluated using the following evaluation criteria.

5...Almost no stickiness, 3... Slightly sticky, 1...There is some stickiness.

(Residual degree of residue) After the mold release test was performed for the fourth time, the degree of residue remaining in the blended mold was visually judged according to the following evaluation criteria.

5... Almost no residue left, 3...There is a little bit of waste left, 1...There is some residue.

Example 1 Nonionic surfactant polyoxyethylene tridecyl ether N~1 is added to the fluorine-containing organosilicon compound represented by the formula
310 [Nippon Nyukaza ■ product name] and viscosity is 350
Nonionic surfactant N-1 containing cS dimethyl silicone oil and F1a [part name manufactured by Shin-Etsu Chemical Co., Ltd.]
The emulsified product in 310 was added in the amount shown in Table 531 and dispersed in water to form a mold release agent A-I with the concentration shown in Table 1.
For comparison, the nonionic surfactant N-
1310 was used to emulsify and adjust the concentration to prepare mold release agent J-L.

Then, a mold release test during epoxy resin molding was conducted using the mold release agent A-L thus obtained, and the results shown in Table 1 were obtained.

Example 2 A fluorine-containing organosilicon compound represented by the formula was mixed with a surfactant, polyoxyethylene nonylphenyl ether, Emulgen 909 [trade name manufactured by Kao Corporation], 0°5 parts of hexamethyldisiloxane, and octamethylcyclotetra. Siloxane 3
5 parts of sodium lauryl sulfate/SLS (trade name manufactured by Nikko Chemicals ■) and 64 parts of water were emulsion-polymerized (viscosity 350C5) in the amounts shown in Table 2 and dispersed in water. The mold release agent M- shown in Table 342
In addition to making U, the above silicone oil emulsion polymerization amount and methyl silicone face KR-2 were used for comparison.
51 [Name of part manufactured by Shin-Etsu Chemical Co., Ltd.] 1 part of the above-mentioned surfactant Emulgen 9090.1 part was used to emulsify the silicone face emulsion product, which was then dispersed in water to make mold release agents V and W. The mold release agent M-W obtained in this way is impregnated into gauze, and the mold release agent is applied onto an aluminum plate using this gauze.
After air drying, the following composition was placed on the aluminum plate: 68.6 parts of polyol (liquid G), 30.2 parts of blowing agent, 0.2 parts of triethylenediamine, 1.0 part of dimethylethanolamine, and Mol-based isocyanate (liquid H).
A urethane resin composition consisting of 50 parts was thoroughly mixed and poured, left at room temperature for 10 minutes, and then heated at 105°C for 10 minutes to cure.The cured product was peeled off from the aluminum plate, and the mold release performance at that time was measured by hand. The stickiness of the molded product was also evaluated by touch, and the results shown in Table 2 were obtained.

(Note) ◆l Type I property criteria 5...Easy to remove with almost no resistance, 4...Some resistance, 3-...Resistance, 2...Partial adhesion, 1...・Full surface adhesion [Effect of the invention] The present invention relates to a new mold release agent, which is a mold release agent that dissolves or disperses a fluorine-containing organosilicon compound represented by the general formula (1) as described above in an aqueous medium. However, since the fluorine-containing organosilicon compound used here has a siloxane bond as an intermediary between the perfluoroalkyl group and the polyether group, synthetic resins, rubber, etc. It has excellent mold releasability that allows the mold to be used repeatedly when molded, and when releasing the adhesive synthetic resin from the mold, no residue of the molded product adheres to the mold and remains. Even though it is water-based, it has very good wettability when applied to the mold, and can evenly wet the mold surface.Furthermore, because it is water-based, it is safe, hygienic, and easy to handle and manage. It has this advantage.

hand Continued Neho Positive book 1990 May 8th day 2゜ name of invention away mold agent 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_f is a fluoroalkyl group having 4 to 20 carbon atoms, and R^1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms. , R^2 is a hydrogen atom or the same monovalent hydrocarbon group as R^1, A and B are divalent organic groups, m is an integer from 1 to 3, x is 2 or 3
, y is an integer of 1 to 50) is dissolved or dispersed in an aqueous medium. 2. A composition containing at least one selected from silicone oil, silicone varnish, and surfactant in the fluorine-containing organosilicon compound shown in claim 1 is dissolved or dispersed in an aqueous medium. A mold release agent that is characterized by its properties.