JPH07246624A - Releasant - Google Patents

Abstract

PURPOSE:To provide releasant, which has no trouble in fabrication quality, poor electrical contact or the like of a molded article and is excellent in mold releasing performance. CONSTITUTION:The effective component of releasant is graft copolymer, which is produced by graft-copolymerizing fluorinated alpha-olefin, which is represented by the general formula RfCH=CH2, in which Rf is 4-20C polyfouorocarbon group, with polyalkylene glycol or its alkyl ether.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a release agent. More specifically, it relates to a mold release agent having excellent mold releasability.

[0002]

2. Description of the Related Art Silicone, wax, talc, mica, PTFE and the like have been known as mold releasing agents, but silicone and wax have good mold releasing properties. However, there are drawbacks such as a decrease in paintability and secondary workability due to the shift to a molded product, lack of durability, and a short mold release life. With PTFE, the durability of mold release effect and secondary processability are On the other hand, although it is good, it has a drawback that it takes time and labor such as baking on the mold surface at the time of releasing treatment.

As a release agent for compensating for these drawbacks, a release agent containing a perfluoroalkyl group-containing phosphate ester (salt) and silicone oil or silicone varnish as essential components has been proposed (Japanese Patent Publication No. 53-23270- No. 1 gazette, the same
57-48035), these mold release agents are excellent in mold release performance, but since they use a silicone compound in combination, there are problems in electrical contact failure, secondary processability and the like.

Further, a releasing agent containing a polyfluorocarbon group-containing phosphonic acid (salt) and a wax as essential components has been proposed (Japanese Patent Publication No. 3-78244), but also in this case, there is a problem in secondary processability. In addition, it is necessary to wash with a solvent such as 1,1,1-trichloroethane after molding.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a mold release agent which is free from problems such as secondary workability of molded products and defective electrical contacts and has excellent mold release performance. .

[0006]

The object of the present invention is as follows.
Graft copolymerization obtained by graft-copolymerizing a fluorinated α-olefin represented by the general formula RfCH = CH ₂ (where Rf is a polyfluorocarbon group having 4 to 20 carbon atoms) with polyalkylene glycol or its alkyl ether. This is achieved by a release agent containing coalescence as an active ingredient.

The polyalkylene glycol, which is the backbone polymer of the graft copolymer, has the general formula R ₁ O (RO) nR ₂ (wherein R is an alkylene group having 2 to 4 carbon atoms, R ₁ is a hydrogen atom or Is a methyl group, R ₂ is a hydrogen atom, carbon number 1-20
Is an alkyl group or an aralkyl group, and n is 1 to
Is an integer of 50), for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., or those whose end groups are etherified with a lower alkyl group such as a methyl group, generally monoetherified, etc. Used.

Fluorine used as a graft comonomer
As the oxidised α-olefin, Rf group is a poly (C 4-20)
Fluorocarbon group, preferably a C6-C12 perf
What is a luoroalkyl group,
From the standpoint of mold release performance, the fluorine content in the resulting graft copolymer is
Elemental content of about 3 to 70% by weight, preferably about 10 to 50% by weight
Used in such an amount that Such fluorinated α-olefin
Examples of the tin include the following compounds. C₆F₁₃CH = CH₂  C₈F₁₇CH = CH₂  C_TenF_{twenty one}CH = CH₂  Cl (CF₂) nCH = CH₂(n: 4 ~ 20) H (CF₂) nCH = CH₂(n: 4 to 20) CF₃(CF₂) n (CH₂) mCH = CH₂(n: 4 to 18, m: 1 to 4)

The graft copolymerization reaction between these two is carried out, if necessary, with a solvent such as benzene and a peroxide system,
It is possible to obtain a graft copolymer which is considered to have been graft-copolymerized with a fluorinated olefin to the terminal alkylene glycol group by heating to a temperature of about 80 to 180 ° C using a radical initiator such as an azo type. it can.

The obtained graft copolymer is used as a release agent in a state of being dissolved or dispersed in an organic medium or an aqueous medium. Examples of the organic medium include xylene,
Aromatic hydrocarbons such as toluene, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, methyl chloroform, xylene hexafluoride, 1,1,2 -Halogenated hydrocarbons such as trichloro-1,2,2-trifluoroethane, etc. are used, and these are separated as a graft copolymer solution having a concentration of about 0.01 to 30% by weight, preferably about 0.05 to 3% by weight. A mold is prepared. Also, when an aqueous medium is used, the release agent is prepared as a dispersion liquid in which the graft copolymer is dispersed at the same concentration.

Japanese Patent Publication No. 2-45572 with a graft copolymer
As disclosed in Japanese Patent Publication No. 3-78244, the general formula RfR
PO (OH) ₂ (wherein Rf is a polyfluorocarbon group having 4 to 20 carbon atoms, and R is an alkylene group having 1 to 3 carbon atoms) and a phosphonic acid containing a polyfluorocarbon group or a salt thereof is used in combination. Then, the mold release performance, sustainability, secondary workability of the molded product, and the like are further improved.

Such a polyfluorocarbon group-containing phospho
Examples of the acid include the following compounds. C₈F₁₇(CH₂)₂PO (OH)₂  C_TenF_{twenty one}(CH₂)₂PO (OH)₂  (CF₃)₂CF (CF₂CF₂) n (CH₂)₂PO (OH)₂  (CF₃)₃C (CF₂CF₂) n (CH₂)₂PO (OH)₂  [n: 2 to 4] Further, as phosphonates, metal salts, amine salts,
A monium salt or the like is used.

The graft copolymer and phosphonic acid (salt) are
In the total amount of both, phosphonic acid (salt) is about 50% by weight or less, preferably about 40 to 10% by weight, particularly preferably about 40 to 30% by weight.
And the total concentration thereof is within the above range.

In this way, the release agent prepared as a solution or dispersion of the graft copolymer or the graft copolymer and the phosphonic acid (salt) in an organic medium or an aqueous medium is spray-coated, brush-coated, It is applied by means such as dipping. Further, this release agent can be applied to other than the mold surface, for example, when applied to the surface of rubber cloth,
Effectively prevent sticking of the dough.

[0015]

The release agent according to the present invention has the following effects. (1) Even at a low concentration of about 0.1% by weight, excellent mold releasability and sustainability are exhibited, so that mold stains due to the mold release agent can be reduced and dimensional accuracy of molded products can be improved. (2) There is no problem of defective electrical contact of the molded product, and it has excellent secondary workability. (3) When used in combination with a polyfluorocarbon group-containing phosphonic acid (salt), in particular, releasability, lubrication performance, remarkably improved life of releasability, migration of the release agent component to the molded product is small, It is also excellent in secondary workability.

[0016]

EXAMPLES The present invention will now be described with reference to examples.

Example 1 (Production Example of Graft Copolymer) 192.70 g (1.284 mol) of triethylene glycol was placed in a reaction vessel having a capacity of 300 ml equipped with a stirrer, a reflux device and a thermometer, and heated to 70 ° C. After warming, nitrogen gas replacement was performed for 30 minutes. After that, the temperature was raised to 170 ° C., 1.25 g of di-tert-butyl peroxide was added, and the mixture was stirred and mixed for 5 minutes, then 57.30 g (0.128 mol) of perfluorooctylethylene C ₈ F ₁₇ CH═CH _{2 was} taken over 1 hour. 2 drops at that temperature
The reaction was carried out for 4 hours. After completion of the reaction, unreacted triethylene glycol, perfluorooctylethylene, decomposition products of the initiator, etc. were removed under reduced pressure to obtain a graft copolymer having the following structure.
75 g (yield 30%) was obtained as a highly viscous pale yellow transparent liquid. ¹ H-NMR analysis: [Products] a and b peaks disappeared d peaks decreased f: New peak appearance at 2.9 ppm and g: 2.3 ppm Integration ratio c d e f g (product) 2 2.2 8 0.9 4.2 (theoretical value) 2 2 8 1 4 Infrared absorption spectrum: 3400 cm ^-1 (O-H stretching) 2900 cm ^-1 (C-H stretch) 1100 cm ^-1 (C-O stretch) 1200 cm ^-1 (C-F stretch) Elemental analysis (fluorine content): Found 55.0% Theoretical value 54.2%

Example 2 (Production Example of Graft Copolymer) Polyethylene glycol monomethyl ether (molecular weight 200
200.75 g (0.100 mol) (0, melting point 48 ° C.) were charged into a reaction vessel having a capacity of 300 ml equipped with a stirrer, a reflux device and a thermometer, heated to 70 ° C., and then purged with nitrogen gas for 30 minutes. .
After that, the temperature was raised to 145 ° C and di-tert-butyl peroxide 1.
After adding 25 g and stirring and mixing for 5 minutes, perfluorooctylethylene 49.25 g (0.110 mol) was added dropwise over 2 hours,
The reaction was carried out at that temperature for 24 hours. After the completion of the reaction, the same treatment as in Example 1 was performed, and the melting point was estimated to be 56 ° C.
234g of pale yellow waxy graft copolymer (yield 93%)
Obtained. Elemental analysis (fluorine content): Measured value 13.7% Theoretical value 14.3%

Example 3 (Preparation of release agent) Release agent A: C ₈ F ₁₇ CH = CH ₂ graft copolymer to polyethylene glycol (average molecular weight 300) (weight ratio 40/60, fluorine content 43.3 0.5% by weight xylene hexafluoride 99.5 parts by weight Release agent B: C ₈ F ₁₇ CH = CH ₂ graft copolymer to polyethylene glycol (average molecular weight 2000) (weight ratio 80/20, fluorine content 14.5) 0.5% by weight Water 99.5 parts by weight Release agent C: C ₈ F ₁₇ CH = CH ₂ graft copolymer to polyethylene glycol (average molecular weight 6000) (weight ratio 92/8, fluorine content 5.8% by weight) 0.5 parts by weight Water 99.5 parts by weight Release agent D: C ₈ F ₁₇ CH = CH ₂ graft copolymer to polypropylene glycol (average molecular weight 2000) (weight ratio 80/20, fluorine content 14.5% by weight) 0.5 parts by weight Isopropyl alcohol 99.5 parts by weight Release agent E: Polyethylene glycol monomethyl ether (NOF Corporation) Goods Uniox _{M-200 0, C 8 F} 17 CH = CH 2 graft copolymer (80/20 by weight, the fluorine-containing Yuritsu 14.5 wt%) 0.5 parts by weight of water 99.5 parts by weight Releasing to average molecular weight 2000) Agent F: Graft copolymer used in release agent B 0.3 parts by weight C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH) (ONa) 0.2 parts by weight water 99.5 parts by weight Release agent G: Release agent E Graft copolymer used in Step 0.3 C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH) (ONa) 0.2 parts by weight Water 99.5 parts Release agent H: Graft copolymer used in release agent B Combined 0.1 parts by weight C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH) (ONa) 0.05 parts by weight Water 99.85 parts by weight Release agent I: Graft copolymer obtained in Example 1 (weight ratio 77/23, Fluorine content 55.0% by weight) 0.5 parts by weight xylene hexafluoride 99.5 parts by weight Release agent J: Graft copolymer obtained in Example 2 (weight ratio 80/20, fluorine content 13.7% by weight) 0.5 parts by weight Water 99.5 parts by weight

Using these mold release agents, the following mold release test was conducted to evaluate the mold release performance. [Mold releasability] 100 parts by weight of polyurethane prepolymer (Coronate C-4090 manufactured by Nippon Polyurethane Industry Co., Ltd.) heated to 80 ° C and methylene-bis-o-chloroaniline curing agent heated and melted (Ihara Chemical product Ihara Cure (Min MT) 12.8 parts by weight while stirring and mixing so as not to entrap air bubbles, and mix this mixture in a mold (a diameter of 45 mm, a depth of 50 mm) made of aluminum with a release agent spray preheated to 80 ° C. Inject. A hook for taking out the cured molded product is set up in the center of the space of the mold, heated and cured at 120 ° C for 1 hour, and then the hook is pulled to remove the molded product from the mold. Obtain the mold release load at that time. [Release life] After determining the mold releasability as described above, how many times it was possible to release under a release load of 5 kgf or less by applying this release agent once. taking measurement. [Paintbullability] The state when the oil-based magic ink is applied to the surface of the molded product obtained by the measurement of the mold releasability is evaluated according to the following criteria. A: No repellency B: Partially repellant C: Significant repellency D: Ripple cannot be written [Paint adhesion] On the surface of the molded product obtained by the above mold releasability measurement, lacquer spray (atom) After spray coating the chemical paint product aerosol lacquer sky blue) and drying,
Whether or not it could be peeled off with cellophane tape was evaluated according to the following criteria. A: No peeling at all B: Some peeling off C: Peeling off considerably D: All peeling off

The above measurement results are shown in Table 1 below.
No problem of defective electrical contacts was found in any of the molded products. Table 1 Release agent Mold release property (kgf) Release life (times) Paintable paint adhesion A 0.4 9 BB B 0.3 8 〃 C 〃 7 〃 〃 D 〃 〃 〃 E 0.2 10 〃 〃 F 0.0 13 A 〃 G 〃 16 〃 〃 H 〃 8 〃 A I 0.2 9 BB J 0.3 8 〃 〃

Comparative Example Release Agent K: C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH) (ONa) 0.5 parts by weight Water 99.5 parts by weight Release Agent L: C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH ) (ONa) 0.2 parts by weight Silicone oil emulsion (LE-45, 35% water dispersion of Nippon Unicar) 0.85 parts by weight Water 98.95 parts by weight Release agent M: C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH) ( ONa) 0.2 parts by weight Silicone varnish emulsion (Shin-Etsu Silicone KS707, prepared with a surfactant from 50% toluene solution, 12.5% water dispersion) 2.4 parts by weight Water 97.4 parts by weight Release agent N: C ₈ F ₁₇ (CH ₂ ) ₂ PO (OH) (ONa) 0.2 parts by weight Wax emulsion (prepared from Mitsui Petrochemical's High Wax 4202E using surfactant, 24% water dispersion) 1.66 parts by weight Water 98.14 parts by weight Release agent O : Silicone emulsion (Japan Unicar LE-45, 35% water dispersion) 50 parts by weight Water 50 parts by weight

Using these release agents, a releasability test similar to that of the embodiment was conducted, and the measurement results shown in Table 2 below were obtained. Table 2 Release agent Mold release property (kgf) Release life (times) Paintable paint adhesion K 1.3 5 AA L 0.0 8 CC M 0.1 11 AB N 〃 6 CC O 〃 3 DD Release agent M However, although it shows a good mold release performance, the problem of electrical contact failure remains and it cannot be used as a mold release agent for electrically related molded products.

Claims (4)

[Claims] 1. A fluorinated α-olefin represented by the general formula RfCH═CH ₂ (where Rf is a polyfluorocarbon group having 4 to 20 carbon atoms) is graft-copolymerized with polyalkylene glycol or its alkyl ether. A release agent comprising the graft copolymer thus obtained as an active ingredient. 2. A graft copolymerization of polyalkylene glycol or its alkyl ether with a fluorinated α-olefin represented by the general formula RfCH═CH ₂ (where Rf is a polyfluorocarbon group having 4 to 20 carbon atoms). And the general formula RfRPO (OH) ₂ (wherein Rf is a polyfluorocarbon group having 4 to 20 carbon atoms and R is 1 carbon atom).
A release agent comprising a polyfluorocarbon group-containing phosphonic acid represented by the formula (3) to alkylene group) or a salt thereof as an active ingredient. 3. A fluorinated α-olefin represented by the general formula RfCH═CH ₂ (wherein Rf is a polyfluorocarbon group having 4 to 20 carbon atoms) is graft-copolymerized with polyalkylene glycol or its alkyl ether. Graft copolymer. 4. A graft copolymerization of polyalkylene glycol or its alkyl ether with a fluorinated α-olefin represented by the general formula RfCH═CH ₂ (where Rf is a polyfluorocarbon group having 4 to 20 carbon atoms). A method for producing a graft copolymer, which comprises: