JPS59157190A - Fluorine-containing mold-release agent - Google Patents

Abstract

PURPOSE:To prepare a mold-release agent having high and durable effect to release a molded article of plastic or rubber, etc. from the mold, by compounding a specific fluorine compound containing active hydrogen, a specific fluorine compound containing NCO group and a reaction product of a polyol and an isocyanate. CONSTITUTION:The objective fluorine-containing mold-release agent is composed of (A) (i) a fluorine compound containing active hydrogen atom and represented by formula I [Rf is 1-20C polyfluoroalkyl; A is l-valent organic group (l= m+n); Z is OH, SH or NR<1>)H (R<1> is H or lower alkyl)] and/or (ii) a fluorine compound containing NCO group and represented by formula II [B is l-valent organic group (l=m+n)] and (B) the reaction product of a polyol and an isocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorine-containing mold release agent that has excellent mold release effects and durability for molded products such as synthetic resins and rubber.

Silicone has traditionally been used as a mold release agent for molded products.

Polytetrafluoroethin (pT)
In addition to organic compounds such as ri), inorganic compounds such as Merck, mica, and silica powder are known.

However, the following types of conventional mold release agents are recognized. That is, silicone 1. Although waxes have good mold release and performance, they cannot be used several times in a row after one mold release treatment, and the mold release agent adheres to the surface of the molded product, making it difficult to apply uniform coating or adhesive treatment. Poor secondary processability may be hindered. Although FTPRl has a long-lasting mold release effect and good secondary processability, the mold surface must be heated and baked during mold release treatment, which is time-consuming. Furthermore, in the case of reprocessing, the baked PTFE must be peeled off, which requires a great deal of effort.

As described above, conventional mold release agents have problems in terms of secondary processability and mold release treatment in addition to the basic mold release effect. The inventors of the present invention have conducted extensive research to develop a mold release agent that has good mold release properties as well as good secondary processability and mold release processability, and have developed the following new fluorine-containing mold release agent. I was able to find out. That is, the present invention provides active hydrogen group-containing fluorine compounds represented by the following general formula <1) and/or the general formula (
The present invention relates to a fluorine-containing mold release agent characterized by comprising a Neo group-containing fluorine compound represented by 11) and a reaction product with a polyol and incyanate.

(Rf)m-A-(z)n...(1)
(R1,)In-B-(Neo)n・
(I) The mold release agent of the present invention does not transfer the mold release agent to molded products, which is the case with silicones and waxes, and can be used for secondary processing such as painting and grouting without post-processing. I can do it as is.

In addition, the mold release agent of the present invention can be easily released by simply dissolving it in an organic solvent or dispersing it in water and applying it to the surface of a mold having a normal mold temperature and drying it. During reprocessing, the mold release agent coating can be easily peeled off with a solvent, and the labor of mold release treatment and reprocessing can be significantly reduced. Furthermore, it forms a tough film that will not melt the release agent film due to the reaction heat during mold molding, and even if a part of the film peels off, it can be partially repaired immediately. be.

The mold release agent of the present invention comprises an addition reaction between an active hydrogen group-containing fluorine compound represented by the general formula (1) and/or a Neo group-containing fluorine compound represented by the general formula (n), a polyol, and an incyanate. It is a product. General formula (
1), Rf in (II) is a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms, and usually a polyfluoroalkyl group is used at the terminal end. Those containing hydrogen atoms or chlorine atoms, or (oxyperfluoroalkylene-containing groups) can also be adopted.
16 perfluoroalkyl groups. General formula (1)
A compound represented by has a bond and a terminal knee o.
Fluorine compounds containing active hydrogen groups such as H, -sH, or -N(R1)H are preferred. Also, general formula (■)
The compound represented by is preferably a fluorine compound containing at least one O group.

A specific example of the general formula (1) is NH(3ON
(C2H4NH2)2 Rfc6u(a2n4oH)2 1) 1) PmILI
Siri 9 @ both Rf
C2H40CONH(cH2)6to(coNH(cH2)
)6Nco)2.

As polyols, polyester polyols, polyether polyols, and other polyols can be used. Examples of polyester polyols include polyester polyols which are reaction products of polybasic acids and polyhydric alcohols, and ring-opened polymers of cyclic esters. The reaction product of a polybasic acid and a polyhydric alcohol is preferably one obtained by the reaction of a polybasic acid, a polybasic acid derivative such as its anhydride, its acid halide, or its ester, and a polyhydric alcohol. Examples of polybasic acids include adipic acid, conophosphoric acid, and azelaic acid.

Sebacic acid, phthalic acid, isophthalic acid 1. Terephthalic acid and other aliphatic or aromatic dicarboxylic acids are suitable. Polyhydric alcohols include ethylene glycol, ethylene glycol, propylene glycol,
Dipropylene glycol, butylene glycol, 1.4
-butanediol, neopentyl glycol, 1.6-
Hexanediol, other diols, glycerin.

Trimethylolpropane, hexanetriol.

Other triols, pentaerythritol.

Diglycerin and other polyhydric alcohols having a valence of 4 or more are suitable, and the above-mentioned diols and triols are particularly suitable. Two or more of these polyhydric octacids and polyhydric alcohols can be used in combination. Suitable polyester diols are reaction products of dicarboxylic acids and diols, and trivalent or higher polyester polyols are suitably reaction products of dicarboxylic acids and triols, or even diols. The hydroxyl value of the polyester polyol is not particularly limited, but is approximately 20 to 800, particularly approximately 100 to 600.
is appropriate.

As a polyether polyol, a cyclic ether such as an epoxide is added to a compound (hereinafter referred to as an initiator) having at least two hydrogen atoms (i.e., hydrogen atoms such as water, hydroxyl group, amino group, amide group, etc.) to which an epoxide can be added. A polyether polyol obtained by adding is suitable. i.e. water, polyhydric alcohols as mentioned above.

Polyphenols and monoamines such as novolak.

It is a polyether polyol obtained by adding epoxide or tetrahydrofuran to a polyamine, polyamide, urea, melamine, phosphate ester, or other initiator. Examples of epoxides include ethylene oxide, propylene oxide, butylene oxide, etc. having 2 to 4 carbon atoms.
Preferred are alkylene oxides, but this is not limiting; halogenated alkylene oxides such as epichlorohydrin, styrene oxide, glycidyl ethers, glycidyl esters, and other epoxides may also be used. Two or more types of initiators and cyclic ethers can also be used in combination. Its hydroxyl value is not particularly limited, but about 20 to 800, especially about 100 to 6
00 is appropriate.

Other polyols include hydrocarbon polymers having two or more hydroxyl groups, such as polybutadiene glycols, polyether ester polyols, polycarbonate polyols made of butadiene homopolymers, copolymers with comonomers such as acrylonitrile and styrene, etc. etc. will do it. These polyester-saving polyesters.

Two or more kinds of polyether polyols and other polyols can be used in combination.

Also, in some cases, those low molecular weight polyols,
For example, a polyhydric alcohol can also be used in combination.

As the isocyanate, well-known aliphatic, alicyclic, or aromatic mono- or polyisocyanates can be used, but from the viewpoint of curing speed and film toughness, aromatic polyisocyanates or aromatic aliphatic Mixed group polyisocyanates are preferred. For example, CO H3 a3 can be mentioned.

If all of the incyanate groups do not need to be subjected to an addition reaction with a fluorine compound or polyol, the remaining incyanate groups can be treated with alcohols, amines, etc., which are commonly used as blocking agents for incyanate groups. Or block it with amides etc.

1 of the fluorine compounds in the mold release agent/solid content of the present invention
Publication □combined'' is 'Usually 1 part per 00 parts of solid content of mold release agent.
0 to 90 parts, preferably 30 to 70 parts ii;'
It's right.

The molding agent of the present invention can be sprayed onto the mold surface by dispersing it in water or dissolving it in an organic solvent.
The mold is released by brush coating or by dipping the mold in the solution. Examples of organic compounds include ketone necks such as acetone and methyl ethyl ketone, ethers such as diethyl ether and dioxane, and esters such as ethyl acetate.

Methyl chloroform, chloroethylene, tetrachloroethylene, tetrachlorodifluoroethane, 1,
One or a mixture of two or more halogenated hydrocarbons such as 1,2-trichloro-1,2,2-to-1-7-fluoroethane may be employed. If a propellant such as dichlorodifluoromethane, monofluorotrichloroethane, or dichlorotetrafluoroethane is added to such a solution to form an aerosol, spray treatment and mold release treatment become easier. The amount of the mold release agent of the present application in the solvent is usually 0.1
~10 weight scale, preferably 1~5 weight scale.

The mold release agent of the present invention can form a mold release coating film with high durability and mold release properties simply by applying it to the inner surface of a wooden mold, metal mold, or synthetic resin mold and drying it. It also has excellent film-forming properties and can form a uniform coating on complex-shaped mold surfaces or large mold surfaces. Furthermore, since there is no need to apply thick coating, the dimensional accuracy of the molded product is improved. On the other hand, since the mold release agent of the present application can withstand repeated use for 7 times, the number of times of reprocessing is small, and the labor of mold release treatment is reduced, which improves the productivity of molded products.

For reprocessing, use acetone, methyl chloroform.

Trichlorethylene, 1,1.2-)dichloro-1゜2
, 2-) The release coating film can be easily removed with a solvent such as refluoroethane, and there is little need for new release treatment. Part of the application
Molded objects that can be molded using a molding agent include rubber, thermoplastic, or thermosetting resin.

or fiber-reinforced synthetic resin, or other inorganic molded bodies. Particularly when molding resins that have high reactivity and easily react with mold release E, such as urethane resin, the release π1! The drug is effective.

The ability output side of the present invention will be further explained below, but the present invention is not limited to this explanation in any way.

Example of synthesis of fluorine compound containing ROM group or NOO group” 300 equipped with a stirring device, thermometer, cooling tube, and dropping funnel
17.4 t (0.1 mole) of 2.4'-)ylene diisocyanate-' and diglyme 207 were placed in a fourth flask. Inside the flask 70-80℃
Keep Rf02H40H51,4? (Q, 1.mo
le) was added dropwise over 3 hours, and stirring was continued for 2 hours.

The above reactor was assembled separately and jetanolamine 10
．． 5 t (0.1 mole) was added. The inside of the flask was maintained at 70 to 80°C, and the above product was added dropwise over 3 hours, followed by further stirring for 2 hours. Thereafter, N was produced by reprecipitation.

II (by which it was confirmed that the NCO group (2250 on-'') of the raw material was dissipated. Yield: 71.8? (90 units) In this way, the following compound (1) was synthesized.

In addition, the following compounds (1) to (2) were synthesized by the same method.

■ RfCON (02H40H) 2 Example The mold release agent of the present invention consisting of each of the compounds of the above ■ to ■, a polyol (Tesmofene 800, Sumitomo Bayer Urethane), and an isocyanate (Desmodur HIJ, Jusumo Bayer Urethane) was used, respectively. A treatment solution was prepared by dissolving it in a solvent. This treatment liquid was 300×30Gwa,
It was applied to an aluminum mold with a depth of 3 elbows and kept at 65°C for 30 minutes to dry and harden.

A urethane resin having the following composition was injected at 65°C, and the molded product was taken out after 3 minutes. Furthermore, this injection and demolding operation was repeated until it became impossible to release the mold, and the number of times it continued was measured, and the results shown in Table 1 below were obtained.

Composition of urethane resin for testing Table 1 + Based on JIS K 5401 pencil scratch test.

The ratio of fluorine compound to 100 parts of solid content of mold release agent is 1'jU, 20 parts of mold agent ■', ■', other ■
~■ are 10 copies each.

Claims (1)

[Claims] 1. An active hydrogen group-containing fluorine compound represented by the following general formula (Natsu) and/or an NC represented by the following formula (II)
O group-containing fluorine compounds and polyols. A fluorine-containing mold release agent characterized by being composed of a reaction product between the fluorine-containing mold release agent and incyanate.
)n...(1)(Rf)m-B-・(Woo)n-・
-(II)2. The fluorine-containing mold release agent according to claim 1, wherein the incyanate is an aromatic polyisocyanate or an aromatic aliphatic mixed polyisocyanate.