JPH09109158A - Incombustible molding release agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a universal molding release agent composition having no flash point without using ozone destructive substance, no adherence of dust to obtain an excellent releasability and having paintability and no substrate selectivity. SOLUTION: The release agent composition comprises 0.01 to 10.0wt.% of fluorine-containing oil or fluorine-containing polymer as solute content, 30.0wt.% or more of nonignitable perfluoro organic compound as liquid content, and no flash point.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as CF
C113), 1,1-dichloro-1-fluoroethane (hereinafter abbreviated as HCFC141b), 1,1,1-
A new fluorine-based non-combustible material with excellent properties as a mold-release agent, rust preventive and water / oil repellent that replaces a fluorine-based non-combustible mold release agent containing trichloroethane and other organic chlorine solvents as solvent components. And a mold release agent composition for molding.

[0002]

2. Description of the Related Art Chlorofluorocarbons have low toxicity, are often nonflammable and chemically stable, and since various types having different boiling points are available, they have been used in many industrial fields. It was Among them, CFC113
Is a degreasing solvent for many plastic materials, some rubber materials, various composite materials, etc.
It has been used as a dispersion medium or diluent.

Like CFC113, 1,1,1-trichloroethane is also used in various industrial fields because of its properties such as low toxicity, chemical stability, nonflammability, and low boiling point.

On the other hand, the fluorine-based non-combustible mold release agent has the excellent property that it can be used anywhere because it has the paintability and the non-flammability which are weak points of the silicone-based mold release agent. It is often used as a mold / rust inhibitor or water / oil repellent. Many of these fluorine-based release agent compositions, the active ingredient consisting of a fluorine-based resin having a releasing property, rust preventive property and water / oil repellency, a fluorine-based oil, or a mixture thereof, and the active ingredient are dissolved, It is composed of a component to be dispersed or diluted, and as the component to be dissolved, dispersed or diluted, the above-mentioned chlorofluorocarbon, 1,
1,1-Trichloroethane or a mixture containing at least one of them has been often used.

[0005]

In recent years, ozone holes have been discovered due to changes in the global environment, and it has become clear that the main cause of this is the organochlorine compounds. Chlorofluorocarbons, which are chemically particularly stable, have a long lifetime in the troposphere and diffuse to reach the stratosphere where they are decomposed by sunlight and generate chlorine radicals. These chlorine radicals combine with ozone in the stratosphere to destroy the ozone layer. Therefore, the use of organic chlorine compounds including chlorofluorocarbons tends to be restricted or prohibited internationally.

Among them, CFC 113 has a high ozone depletion potential and early replacement is desired, and a strict reduction schedule is set. Also, for 1,1,1-trichloroethane, a strict reduction schedule is set for the same reason. In addition, HCFC141b has begun to be used due to the regulation of chlorofluorocarbons with a high ozone depletion potential.
Initially, hydrochlorofluorocarbons, etc., attracted attention as second-generation CFCs, but some of them have ozone depletion potentials that are too high to be ignored compared to conventional chlorofluorocarbons, and they have a relatively generous schedule. However, an international use reduction schedule was set up.

Therefore, the object of the present invention is to provide the chlorofluorocarbons 1, 1, which have been conventionally used in such a background.
It is an object of the present invention to provide a novel fluorine-based releasing agent composition which is characterized by not containing 1,1-trichloroethane and hydrochlorofluorocarbon.

Another object of the present invention is to provide a fluorine-based releasing agent composition having excellent releasing property in various plastic molding.

It is another object of the present invention to provide a rust preventive composition and a water / oil repellent composition suitable for protecting and modifying the surface of various substrates.

Another object of the present invention is to provide a non-combustible fluorine-based mold release agent composition having the above-mentioned excellent characteristics.

[0011]

The above object is achieved by the present invention described below. That is, the present invention is characterized by containing a solvent composition containing a non-flammable perfluoroorganic compound in an amount of 30% by weight or more, and a fluorinated oil or a fluorinated polymer in specific amounts, respectively. It is a composition.

That is, a composition containing 30.0% by weight or more of a non-flammable perfluoroorganic compound as a liquid component and having no flammability is used as a component for dissolving, dispersing or diluting an active ingredient. The release agent composition can have the same performance as that of the chlorofluorocarbon, 1,1,1-trichloroethane, hydrochlorofluorocarbon and the liquid component containing them.

Further, 0.01% of a fluorine-containing compound or a fluorine-containing polymer is added to the above releasing agent liquid component as an active ingredient.
To provide an all-purpose non-combustible mold release agent composition that does not contain ozone-depleting substances, has paintability, is non-flammable, and is compatible with various plastic materials by containing -10.0 wt%. You can

[0014]

Next, the present invention will be described in more detail with reference to preferred embodiments.

Chlorofluorocarbons, especially CFC11
The reason why 3 has been frequently used as a liquid component of a release agent composition is that a) it has excellent chemical stability and is unlikely to decompose, and b) it has low toxicity and has a flash point and an ignition point. In other words, high work stability, c) low polarity, does not damage various plastic materials, and at the same time dissolves or disperses fluorine-containing compounds or polymers, d) high vapor pressure and drying speed It depends on the nature of being fast.

The reason why 1,1,1-trichloroethane has been used is mainly because a) it has low toxicity, has no flash point and ignition point, and has high work stability, and b) it has low polarity. Since it does not contain water, it does not damage the mold (the possibility of rusting is low), and at the same time dissolves, disperses or dilutes the fluorine-containing compound or the fluorine-containing polymer, c) has a high vapor pressure, It depends on the property such as high drying speed.

Further, hydrochlorofluorocarbon,
In particular, the reason why HCFC141b is used is as follows: a) low toxicity, no flash point or ignition point, high work stability, b) low polarity, fluorine-containing compound, or fluorine-containing compound Dissolve or disperse the polymer, c) high vapor pressure, fast drying rate, etc.

Therefore, the chlorofluorocarbon,
Similar properties are required to replace 1,1,1-trichloroethane and hydrochlorofluorocarbons.

Therefore, in order to satisfy the above-mentioned required characteristics, various releasing agent compositions have been earnestly studied by paying attention to the low toxicity, nonflammability, nonpolarity, and low chemical attack of perfluoroorganic compounds. Invented.

That is, the release agent composition of the present invention contains, as its liquid component, a non-flammable perfluoroorganic compound which has extremely low polarity, is nonflammable, and does not damage various substrates. . Further, as an effective component of the release agent composition, it contains a fluorinated oil or a fluoropolymer having paintability and excellent releasability for various plastic materials.

Considering that the perfluoroorganic compound used in the present invention does not have a flash point and an ignition point, has a high vapor pressure, has high chemical stability, and has a small chemical attack on various materials, etc. , Perfluoroalkane, perfluorocycloalkane, perfluoroether and / or perfluorocyclic ether and the like are preferable.

More specifically, perfluoropentanes (C ₅ F ₁₂ ), perfluorohexanes (C ₆ F ₁₄ ), perfluoroheptanes (C ₇ F ₁₆ ), perfluorooctanes (C ₈ F) ₁₈₎ perfluorocyclohexane (C ₆ F ₁₂₎ - perfluoro cycloheptane (C ₇ F _14), perfluoro (alkylcyclohexane) (C _{7
F 14, C 8 F 16)} · perfluoro (2-butyl tetrahydrofuran) (C
₈ F ₁₆ O) and the like.

The above-mentioned perfluoro organic compound is contained in an amount of 30.0% by weight or more in the liquid component of the release agent composition of the present invention. If the content is less than this, when a flammable organic compound is additionally contained in a mixed system, a flash point may occur due to the influence of the flammable organic compound, or a plastic material or a mold may be damaged. I will end up.

As the above-mentioned non-flammable perfluoro organic compound, for example, the following commercial products can be used. C ₆ F ₁₄ (Perfluorohexanes) Fluorinert FC-72 Sumitomo 3M Perfluorocarbon Coolant FX3250 〃 Inert Fluid PF5060 〃 Efreed KPF-61 Kanto Denka Kogyo Perfluorohexane PCR C ₇ F ₁₆ (Perfluoroheptanes) Fluorinert FC-84 Sumitomo 3M Inert fluid PF5070 〃 Efreed KPF-71 Kanto Denka Kogyo Perfluoroheptane PCR C ₈ F ₁₈ (Perfluorooctanes) Fluorinert FC-75 Sumitomo 3M Perfluorocarbon Coolant FX3300 〃 Inactive fluid PF5080 〃 Efurido KPF-81 Kanto Denka Kogyo C ₈ F ₁₆ O (perfluoroalkyl tetrahydrofuran) Fluorinert FC-77 available from Sumitomo 3M perfluoro - -Butyl Tetrahydrofuran manufactured by PCR Further, the fluorinated oil or fluoropolymer which is another active ingredient used in the present invention is at least one selected from the group consisting of polychlorotrifluoroethylene derivatives and perfluoropolyethers. Desirably a class of compounds. To give a more detailed example,
The polychlorotrifluoroethylene derivative or perfluoropolyether is preferably a compound represented by the following general formula.

X- (CFClCF ₂ ) _n -X (2≤n≤8) (X = F, Cl) ・ F-((CF ₂ ) ₃ O) _n -C ₂ F ₅ (10≤n≤50) ) Further, when these active ingredients are uniformly spread on the surface of the mold and a good mold releasability is to be obtained, the active ingredient is used in an amount of 0.01% by weight to 10.0% by weight based on all the components. To be Specifically, the range of 0.1 to 5.0% by weight is more preferable. A concentration of 0.01% by weight or more is particularly suitable for obtaining a sufficient releasing property, and a concentration of 10.0% by weight or less makes it possible to remove the active ingredient of the release agent on the resin after injection molding. Is preferable in that it does not remain unnecessarily.

Examples of the above-mentioned fluorinated oil and fluorinated polymer include, but are not limited to, commercially available Daifloyl # 20 manufactured by Daikin Industries, Ltd., Demnum S-20 manufactured by Daikin Industries, and the like.

In the present invention, a general organic solvent or the like may be used in combination depending on the kind of the above-mentioned active ingredient and the kind of other additives.

Examples of the combined solvent include perfluorocarboxylic acid derivatives such as methyltrifluoroacetate, ethyltrifluoroacetate and butylpentafluoropropionate, hexafluorobenzene, pentafluorobenzene, benzotrifluoride and bistrifluoromethylbenzene. Fluorine-containing solvents such as fluorine-containing benzene derivatives, and fluorine-containing alcohols such as trifluoroethanol, pentafluoropropanol and hexafluoroisopropanol are preferable.

Further, the fluorine-based noncombustible mold release agent composition for molding of the present invention may have any other additives as long as it does not have a flash point and does not cause a chemical attack in the resin used. For example, flammable liquids such as isopropanol and toluene may be used as long as the release agent composition does not have a flash point.

The method for treating the fluorine-based noncombustible mold release agent composition of the present invention may be any method such as spray coating, brush coating, dipping and the like. Among them, spray coating is particularly preferable, and specifically, a spraying machine incorporating a molding machine, a spray gun using compressed air, hydrofluorocarbon 134a (hereinafter abbreviated as HFC134a), or the like is used as a propellant. Preferred are aerosols and the like.

[0031]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Example 1-PF5060 [Sumitomo 3M Co., Ltd. (same below)] 99.50% by weight-Daifloil # 20 [Daikin Industries Co., Ltd. (same below)] 0.50% by weight Example 2-PF5060 60. 00% by weight-PF5070 [Sumitomo 3M Co., Ltd. (same below)] 39.00% by weight-Demnum S-20 [Daikin Industries Co., Ltd. (same below)] 1.00% by weight Example 3-FX3250 [ Sumitomo 3M Ltd. (same below)] 50.00% by weight ・ 1,4-bistrifluoromethylbenzene 47.00% by weight ・ Daifloyl # 20 3.00% by weight Example 4 ・ PF5060 40.00% by weight ・1,3-bistrifluoromethylbenzene 24.00% by weight 1,4-bistrifluoromethylbenzene 24.00% by weight Daifloyl 20 2.00 wt% Example 5 PF5060 95.00 wt% Diisopropyl ether 4.00 wt% Daifloyl # 20 1.00 wt% Example 6 PF5060 60.00 wt% 1,3-bistrifluoro Methylbenzene 35.00% by weight-Isopropyl alcohol 3.00% by weight-Daifloyl # 20 2.00% by weight Example 7-PF5060 40.00% by weight-PF5080 [Sumitomo 3M Limited (same below)] 30. 00 wt% -1,4-bistrifluoromethylbenzene 27.00 wt% -Demnum S-20 [Daikin Industries Co., Ltd. (the same applies below)] 3.00 wt% Comparative Example 1-CFC113 83.00 wt%- DAIFREE MS-543 [manufactured by Daikin Industries, Ltd. (hereinafter the same)] 17.00% by weight Comparative Example・ CFC113 77.00% by weight ・ 1,1,1-trichloroethane 20.00% by weight ・ Diefree MS-543 solid content 3.00% by weight Comparative Example 3 ・ HCFC141b 80.00% by weight ・ Diefree GF6330 [Daikin Industries Co., Ltd.] 20.00 wt% Comparative Example 4 PF5060 80.00 wt% CYTOP CTX802S (Asahi Glass Co., Ltd.) 20.00 wt% Comparative Example 5 isopropyl alcohol 80.00 wt% Byax comparison of characteristics of the release agent composition of the AR 20.00% by weight Comparative example 6 high release S-2 (aerosol) [manufactured by Haisoru Corporation] above-described composition ratio is Table 1. principal Ozone Depletion Potential (ODP) of Composition Ozone Depletion Potential
s Releasability Releasability equivalent to the releasability according to the prior art (200 shots or more without clinging) is indicated as ◯. Releasing Agent Remaining The degree of the releasing agent remaining on the surface of the molded product was the same as that of the conventional product, and was marked as “◯”. Adhesion of dust on molded products Whether or not resin dust remains on the surface of the molded product or the mold after molding. A general-purpose plastic for plastic injection molding was subjected to an immersion test to confirm that it had no adverse effects such as dissolution or swelling.

The types of general purpose plastics tested are as follows:

Polysulfone PMMA (acrylic) The test method is as follows. A test piece of the above-mentioned general-purpose plastic cut into a size of 15 × 25 mm is dipped in the release agent composition of each of the above Examples and Comparative Examples for 1 hour. When the weight change rate before and after immersion was less than 1.0% by weight, it was evaluated as ◯, and when it was 1.0% by weight or more, it was evaluated as x. Flammable tag closed automatic flash point tester (RFT manufactured by Riaisha Co., Ltd.)
-101 type) was used and measured in accordance with JIS K2265. A paintable PMMA molded product was adhered with Aron Alpha [manufactured by Toagosei Kagaku Co., Ltd.], and -30 (2 hours) / 70 (2
After 10 hours of heat cycle at (° C.) ° C., the case where peeling did not occur was marked with ◯, and the case where peeling occurred was marked with x.

[0034]

[Table 1]

[0035]

As shown in Table 1 above, according to the present invention, the perfluoroalkyl compound is contained in an amount of 30.0% by weight or more, and 0.01% by weight of a fluorinated oil or a fluoropolymer.
By containing ~ 10.0% by weight, no ozone depleting substance is used, there is no flash point, no dust adheres, good mold releasability is obtained, and paintability is provided and there is no substrate selectivity. A universal mold release composition can be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C10M 147: 02 147: 04) C10N 40:36

Claims (8)

[Claims] 1. A release agent composition comprising a fluorinated oil or a fluorinated polymer as a solute component in an amount of 0.01 to 10.
A non-flammable mold release agent composition for molding, which contains 0 wt% and a non-flammable perfluoroorganic compound as another liquid component in an amount of 30.0 wt% or more and has no flash point. 2. The perfluoro organic compound is 25 ° C.
2. The release agent composition according to claim 1, which is a compound having a vapor pressure of 30 torr or more. 3. The release agent composition according to claim 1, wherein the perfluoroorganic compound is at least one selected from the group consisting of perfluoroalkanes, perfluorocycloalkanes, and perfluorocyclic ethers. 4. The perfluoro organic compound has a molecular formula
C₆ F₁₄Or molecular formula C₇ F₁₆Or molecular formula C₈ F
₁₈Or molecular formula C₆ F₁₂Or molecular formula C ₇ F₁₄Also
Is the molecular formula C₈ F₁₆Perfluoroalkane represented by
Or a perfluorocycloalkane or a mixture thereof.
The release agent composition according to claim 1, which is a compound.
Stuff. 5. The perfluoro cyclic ether has the molecular formula C
₆ F ₁₂ O or molecular formula C ₇ F ₁₄ O or molecular formula C ₈
The release agent composition according to claim 3, which is a perfluoro cyclic ether represented by F ₁₆ O or a mixture thereof. 6. A fluorinated oil or a fluorinated polymer,
The releasing agent composition according to claim 1, which is a compound having a vapor pressure of 50 torr or less at 250 ° C. 7. A fluorinated oil or a fluorinated polymer,
The release agent composition according to any one of claims 1 to 5, which is a compound represented by the following molecular formula, or a mixture thereof. _{X- (CFClCF 2) n -X (} 2 ≦ n ≦ 8) (X = F, Cl) 8. A fluorinated oil or fluoropolymer is
The release agent composition according to any one of claims 1 to 6, which is a compound represented by the following molecular formula, or a mixture thereof. _{F - ((CF 2) 3} O) n -C 2 F 5 (10 ≦ n ≦ 5
0)