JP2526639B2 - Internal release agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an internal mold release agent added to a molding material such as an elastomer and a resin.

2. Description of the Related Art Conventional Techniques and Their Problems Conventionally, two means have been mainly adopted in order to improve the releasability from a mold at the time of molding an elastomer, a resin (hereinafter referred to as a molding material), or the like.

One is a method of forming a release agent coating film by applying an external release agent to a mold during molding. In this case, many releasing agents such as fluorine-based, silicone-based, and wax-based release agents have been developed, and are widely used because they exhibit good releasing property. However, in this method, since a thick release agent coating film is formed on the surface of the mold, the fine unevenness pattern applied to the mold is not restored, and it is difficult to keep the dimensional accuracy of the molded product constant, or In some cases, the mold may be easily soiled due to heat deterioration of the release agent.

Another method is to add an internal release agent to the molding material,
It is a method of kneading and molding. According to this method, the drawbacks found in the method of applying the mold release agent to the mold are eliminated, and since the step of applying the mold release agent to the mold can be omitted, workability is also improved. However, stearic acid and its salts conventionally used as an internal release agent,
Wax, silicone oil, low molecular weight polytetrafluoroethylene and the like do not show sufficient releasability when internally added.

In recent years, a fluorine-based internal release agent containing a fluorine-containing carboxylic acid or the like has been developed (Japanese Patent Application No. 59-213716, JP-A-60).
-58417, JP-A-60-181141). Although this internal mold release agent has a somewhat excellent mold release property, since it is compatible only with a specific molding material, the applicable molding material is limited. In particular, when this internal release agent is added to an elastomer having a strong adhesive property, it does not exhibit sufficient release properties, and an external release agent must be used in combination. In addition, there is a problem that the molded products are adhered to each other, and when the elastomer and the above-mentioned internal release agent are kneaded, stains are remarkably attached to rolls and the like.

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the problems of the above-mentioned prior art, and as a result, 1) an internal release agent containing a certain fluorine-containing compound as an active ingredient is molded. It has excellent compatibility and releasability regardless of the type of material, so it is not necessary to use an external release agent together. 2) Molding by adding the internal release agent Adhesion between them is prevented, and adhesion of dirt to rolls during kneading is reduced, and 3)
The inventors have found that the internal release agent imparts water and oil repellency to a molded product, and completed the present invention.

That is, the present invention is a phosphoric acid ester, thiophosphoric acid ester, phosphonic acid derivative, phosphine containing a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a fluorohydrocarbon group having 1 to 20 carbon atoms and a hydroxyl group. The present invention relates to an internal mold release agent containing one or more selected from the group consisting of acid derivatives and salts thereof as an active ingredient.

In the present invention, the fluorohydrocarbon group having 1 to 20 carbon atoms includes, for example, a fluoroalkyl group having 1 to 20 carbon atoms and a fluoroalkenyl group. Examples of the fluoroalkyl group include a perfluoroalkyl group and an omegahydroperfluoroalkyl group, and a perfluoroalkyl group is particularly preferable. Moreover, as the fluoroalkenyl group, for example, a perfluoroalkenyl group can be exemplified.

In the present invention, the number of carbon atoms used as an active ingredient is 1 to 1.
A phosphoric acid ester, a thiophosphoric acid ester, a phosphonic acid derivative, a phosphinic acid derivative or a salt thereof containing a fluorocarbon group of 20 and a hydrocarbon group of 1 to 18 carbon atoms which may be substituted with a hydroxyl group (hereinafter referred to as Examples of the fluorine compound) include compounds represented by the following general formulas (1) to (3).

[In the formula, R _f represents a perfluoroalkyl group having 6 to 18 carbon atoms or a perfluoroalkenyl group. R represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group. X is an alkylene group having 1 to 10 carbon atoms, a group —CH ₂ CH (O
R ³ ) CH ₂ — or a group —SO ₂ NR ⁴ R ⁵ — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). shown, R ⁵ represents shown.) the alkylene group having 1 to 10 carbon atoms. Y is an alkylene group having 1 to 10 carbon atoms, a group —CH ₂ CH (OR ³ ) CH ₂ one or a group —SO ₂ NR ⁴ R ⁵ — or a group (R ³ , R ⁴ and R ⁵ are the same as above. R ⁶ represents a hydrogen atom, a methyl group or a methoxy group.). M is a hydrogen atom, ammonium group, substituted ammonium group or IA of the periodic table
A metal selected from Group I, Group II A, Group II B, and Group IV B. n and m each represent an integer of 1 or 2, and n + m
≦ 3. In the above general formulas (1) to (3), examples of the hydrocarbon group having 1 to 18 carbon atoms represented by R include a methyl group,
A linear or branched alkyl group having 1 to 18 carbon atoms such as ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, 2-ethyl-hexyl group, stearyl group and lauryl group. Etc. can be illustrated.

Examples of the Group IA metal represented by M include Na and
K, Li, etc. can be mentioned. Examples of Group IIA metals include Ba, Mg, Ca, and the like. II
Examples of the group B metal include Zn and the like. Examples of the IVB metal include Zr and the like.

The substituted ammonium group is substituted with an alkyl group having about 1 to 10 carbon atoms such as monoethylammonium group, monoisopropylammonium group, diethylammonium group, dicyclohexylammonium group, triethylammonium group, di-n-butylammonium group. An ammonium group substituted with a hydroxyalkyl group having about 1 to 10 carbon atoms such as an ammonium group, a monoethanol ammonium group, a diethanol ammonium group, a triethanol ammonium group, and a diisopropanol ammonium group,
Examples thereof include an ammonium group substituted with an aromatic ammonium group such as a pyridinium group.

Examples of the fluorine-containing compound represented by the above general formulas (1) to (3) include the following compounds.

(However, 1 = 3 is 55 mol%, l = 4 is 28 mol%, l = 5
Is 11 mol%, l = 6 is 4 mol%, and l = 7 is 2 mol%. ) (In the formula, M ₁ represents an ammonium group or a substituted ammonium group.) (In the formula, M ₂ represents a metal selected from Group IA, Group II A, Group II B and Group IV B of the Periodic Table.) In addition to the above-mentioned fluorine-containing compound of the present invention, the internal mold-releasing agent of the present invention may contain a fluorine-containing compound other than the above, a hydrocarbon internal mold-releasing agent, and the like. Examples of the fluorine-containing compound other than the above include, for example, R _f -containing carboxylic acid, R _f -containing carboxylic acid ester, R _f -containing polyester, R _f -containing polyether, R _f -containing polyvinyl, and R _f -containing (meth) acrylate oligomer ( R _f is the same as above.) And the like. Known hydrocarbon-based internal release agents can be used, and examples thereof include alkyl phosphates, alkyl sulfonic acids, alkyl carboxylic acids and salts thereof, and waxes.

The amount of the fluorine-containing compound of the present invention in the internal release agent of the present invention is not particularly limited and may be appropriately selected, but is usually 0.00
It may be about 1 to 20% by weight, preferably about 0.01 to 10% by weight. If it is less than 0.001% by weight, the effect of addition is insufficient, while if it exceeds 20% by weight, the physical properties of the molding material may be lower than the permissible range, and the cost is increased. The addition method may be a conventional method, for example, kneading with a roll or the like.

The internal mold release agent of the present invention can be applied to substantially all molding materials. Specific examples thereof include elastomers such as fluororubber, urethane rubber, acrylic rubber and hydrin rubber, and resins such as epoxy resin, phenol resin, melamine resin, olefin resin, polyester and vinyl chloride resin. .

When the internal release agent of the present invention is added to a molding material and kneaded and molded, the above-mentioned fluorine-containing compound of the present invention exudes to the surface of the molding material, and the phosphoric acid group, phosphonic acid group, etc. of the fluorine-containing compound causes the mold surface. The surface of the mold is covered with a perfluorocarbon group to become a low energy surface, and good mold releasability is exhibited. Further, the hydrocarbon group of the fluorine-containing compound improves the compatibility between the molding material and the fluorine-containing compound and uniformly disperses or dissolves the fluorine-containing compound, so that the fluorine-containing compound uniformly exudes.

Effects of the Invention According to the internal mold release agent of the present invention, the following excellent effects are achieved.

1) The internal mold release agent of the present invention, regardless of the type of molding material,
Since it exhibits excellent compatibility and releasability, it is not necessary to use an external release agent together.

2) When the internal mold release agent of the present invention is added and molding is performed, adhesion between molded products is prevented, and adhesion of stains to rolls during kneading is reduced.

3) Since the internal mold release agent of the present invention imparts water and oil repellency to the molded product, the molded product is less likely to become dirty.

Examples The following examples and comparative examples will further clarify the present invention. Hereinafter, when simply referring to “parts” or “%”, it means “parts by weight” or “% by weight”, respectively.

Example 1 1 Purpose The internal release agent of the present invention and a conventional internal release agent were subjected to a release test of semi-rigid urethane foam and fluororubber, and the release performance thereof was measured.

2 Release Agent Used (A) Release Agent of the Present Invention (The composition of i = 3 is 55 mol%, i = 4 is 28 mol%, i = 5 is 11 mol%, i = 6 is 4 mol%, i = 7. Is 1 mol%, X = 1 is 90 mol%, X = 2 is 10 mol%, Y = 1 is 90 mol%, and Y = 2 is 10 mol%.) (The composition of i = 3 is 55 mol%, i = 4 is 28 mol%, i = 5 is 11 mol%, i = 6 is 4 mol%, i = 7. Is 1 mol%.) (The i composition of is the same as) (B) Conventional internal release agent and additive (I has the same composition as, X = 1 is 30 mol%, X = 2 is
70 mol%. ) C ₁₇ H ₃₅ COOH C ₈ F ₁₇ COOH 3 Semi-Rigid Urethane Foam Release Test (A) Composition of Semi-Rigid Urethane Foam Liquid A ・ Polyol (Sumisen 3900, Sumitomo Chemical Co., Ltd.) 90 ・ Water (foaming agent) 1.6 ・ Triethanolamine (Catalyst) 3 ・ Triethylamine (Catalyst) 0.5 ・ Kaolizer (Foam stabilizer, Kao Corporation) 0.5 ・ Internal mold release agent prescribed amount B liquid ・ Isocyanate (Sumijour 44V20, Sumitomo Chemical Co., Ltd.) 41.3 (B ) Test method Semi-rigid urethane foam The above liquid A composition is 1000 rpm x 5 mi
After stirring and mixing, the liquid B was added, and the mixture was stirred and mixed at 5000 rpm × 10 seconds, and immediately poured into an aluminum mold of 6 cmφ × height 3 cm. After curing at room temperature for 10 minutes, tensile tester (pull speed
200 mm / min) is used to measure the release performance by the adhesive strength. The releasability value is a releasability determination value that appears most averagely during measurement.

 The results are shown in Table 1.

4 Mold release test of fluororubber A rubber vulcanization molded product was prepared according to the following composition and vulcanization conditions, and the mold release performance of the surface of the obtained molded product was measured.

Mixture composition Daieru G801 (fluorine rubber: manufactured by Daikin Industries, Ltd.) 100 parts Perhexa 2.5B (crosslinking agent: manufactured by NOF Corporation) 1.5 TYK (triallyl isocyanurate: crosslinking aid: manufactured by Nippon Kasei Co., Ltd.) 4.0 Carbon Black (Thermax, RTVanderbilt Co., Inc.
20) Internal mold release agent Predetermined amount Vulcanization conditions Press vulcanization 160 ° C × 10 minutes Open vulcanization 180 ° C × 4 hours After compounding and kneading with the above composition on a kneading roll, press vulcanization 10 cm × 8 cm A × 2 mm sheet was prepared, and the easiness of removal of the vulcanized molded product from the mold was evaluated according to the following criteria.

A: Almost no force needs to be applied to the mold release.

B: The rubber sticks to the mold a little, so it takes some force to open the mold.

C: Rubber sticks to the mold, and considerable force is required to open the mold.

D: Part of the rubber adhered to the mold.

 The results are shown in Table 2.

From the above results, it is understood that the internal release agent of the present invention has remarkably excellent release performance as compared with the conventional release agents.

Claims (2)

(57) [Claims] 1. A phosphoric acid ester, a thiophosphoric acid ester, a phosphonic acid derivative, or a phosphine containing a C1-C20 fluorohydrocarbon group and a C1-C18 hydrocarbon group which may be substituted with a hydroxyl group. An internal mold release agent containing one or more selected from the group consisting of acid derivatives and salts thereof as an active ingredient. 2. General formula [In the formula, R _f represents a perfluoroalkyl group having 6 to 18 carbon atoms or a perfluoroalkenyl group. R represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group. X is an alkylene group having 1 to 10 carbon atoms, a group —CH ₂ CH (O
R ³ ) CH ₂ — or a group —SO ₂ NR ⁴ R ⁵ — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). R ⁵ represents an alkylene group having 1 to 10 carbon atoms.) M is a hydrogen atom, ammonium group, substituted ammonium group or Group IA, IIA of the periodic table
A metal selected from Group I, Group II B, and Group IV B. n
And m each represent an integer of 1 or 2, and n + m ≦ 3. ] A compound represented by the general formula [In the formula, Y is an alkylene group having 1 to 10 carbon atoms, a group -CH ₂ CH
(OR ³ ) CH ₂ —, group —SO ₂ NR ⁴ R ⁵ — or group (However, R ³ , R ⁴ and R ⁵ are the same as above. R ⁶ is a hydrogen atom, a methyl group or a methoxy group.) R _f , R, M, n and m are the same as above. ] The compound represented by [Wherein R _f , R, X, m and n are the same as above. ] At least 1 selected from the group consisting of compounds represented by
The internal mold release agent according to claim 1, which comprises a phosphoric acid ester, a thiophosphoric acid ester, a phosphonic acid derivative, a phosphinic acid derivative or a salt thereof as an active ingredient.