JP2010214598A - Release agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a release agent which has mold release performance equivalent to that of a release agent containing a compound having ≥8C perfluoroalkyl group as an effective component and contains a compound having ≤6C perfluoroalkyl group which is low in living body accumulation properties as an effective component. <P>SOLUTION: The release agent contains polyfluoroalkyl phosphonic acid expressed by the following formula: C<SB>n</SB>F<SB>2n+1</SB>(CH<SB>2</SB>CF<SB>2</SB>)<SB>a</SB>(CF<SB>2</SB>CF<SB>2</SB>)<SB>b</SB>(CH<SB>2</SB>CH<SB>2</SB>)<SB>c</SB>P(O)(OH)<SB>2</SB>(wherein, n is an integer of 1-6, a is an integer of 1-4, b is an integer of 1-3, and c is an integer of 1-3) or its salt as the effective component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a release agent. More specifically, the present invention relates to a mold release agent having excellent film forming properties and excellent mold releasability.

Currently, release agents such as silicone oil, wax, talc, mica, and tetrafluoroethylene resin are used when polymer materials such as plastic materials and rubber materials are molded using a mold. However, although silicone oil, wax, etc. show good release properties, the release agent moves to the molded product, so the uniform paintability and secondary processability of the molded product are impaired, and the release effect is maintained. Some are lacking in terms of sex. Tetrafluoroethylene resin is satisfactory in terms of sustainability of mold release effect and secondary processability, but it must be subjected to a film-like baking process on the mold surface during the mold release process. In addition, since the same processing is necessary at the time of reprocessing, the number of operation steps increases.

  In order to eliminate such drawbacks, a mold release agent having a polyfluoroalkyl group-containing phosphate ester having 4 to 20 carbon atoms as one of active ingredients has been proposed (see Patent Documents 1 to 3). Although these mold release agents exhibit good mold release properties and have a longer mold release life than conventional ones, they are still used as mold release agents as the shape of molded products has become more complex. There is a need for further improvement in performance.

On the other hand, polyfluoroalkylphosphonic acid esters are also widely used as raw materials for synthesizing active ingredients of release agents. Polyfluoroalkylphosphonic acid releasing agent to release performance when used is easily the most expressed in the compound having a carbon number of 8-12 perfluoroalkyl group, in particular phosphonic acid compounds having a perfluorooctyl group Is
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ P (O) ( OH ) ₂
However, it is preferably used for this kind of application (see Patent Documents 4 to 7).

  By the way, it is reported that phosphoric acid ester or phosphonic acid ester compounds having a C8-12 perfluoroalkyl group are biodegraded in the environment and changed to compounds with relatively high bioaccumulation and environmental concentration. There are concerns about exposure in the treatment process, waste, release to the environment from the treated substrate, diffusion, and the like. In addition, compounds having a perfluoroalkyl group with 14 or more carbon atoms are very difficult to handle because of their physical and chemical properties, and are rarely used in practice.

  Furthermore, the phosphoric acid ester or phosphonic acid ester compound having a perfluoroalkyl group having 8 or more carbon atoms inevitably generates or mixes perfluorooctanoic acids having a high bioaccumulation potential in the production process. Therefore, manufacturers of such phosphoric acid ester or phosphonic acid ester compounds are proceeding withdrawing from the production or replacing them with compounds having a perfluoroalkyl group having 6 or less carbon atoms.

  However, in the compound having 6 or less carbon atoms in the perfluoroalkyl group, the orientation on the surface of the treated substrate is remarkably lowered, and the melting point, glass transition point Tg, etc. are remarkably lower than those in the compound having 8 carbon atoms. It will be greatly affected by environmental conditions such as temperature, humidity, stress, and contact with organic solvents. Therefore, the required sufficient performance cannot be obtained, and the durability is also affected.

Japanese Patent Publication No.53-23270 Japanese Patent Publication No.53-23271 Japanese Patent Publication No.57-48035 Japanese Examined Patent Publication No. 2-45572 Japanese Patent Publication No. 3-78244 Japanese Patent Publication No. 4-4923 Japanese Patent Publication No. 4-11366 WO 2007/105633 A1

  An object of the present invention is a perfluorocarbon having a carbon number of 6 or less, which is said to have a release performance equivalent to that of a release agent containing a compound having a perfluoroalkyl group having 8 or more carbon atoms as an active ingredient and low bioaccumulation. An object of the present invention is to provide a release agent comprising a compound having an alkyl group as an active ingredient.

The object of the present invention is to provide a general formula
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b (CH ₂ CH ₂ ) _c P (O) (OH) ₂ (I)
Wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3, or a salt thereof. This is achieved by a release agent as an active ingredient.

When released into the environment, the polyfluoroalkylphosphonic acid or salt thereof, which is an active ingredient of the release agent according to the present invention, is deHFed at the -CH ₂ CF ₂ -bonding moiety in the molecule to form a double bond. Is formed, and it has a structure that is easily decomposed into compounds with low environmental concentration, bioaccumulation, etc. due to ozonolysis, etc., and perfluoroalkyl carboxylic acids with 8 or more carbon atoms in the production process Do not generate environmentally hazardous substances.

  Such a polyfluoroalkylphosphonic acid or a salt thereof is applied to a mold release object, for example, a mold, even when it is prepared as an aqueous or organic solvent-based mold release agent at a concentration of about 0.1% by weight or less. There is an excellent effect that sometimes shows effective release performance. This is due to the fact that the polyfluoroalkylphosphonic acid or its salt exhibits extremely good solvent solubility, far more than the conventional mold release agent prepared so that the solid content concentration is 0.5% by weight. A release agent exhibiting excellent releasability can be obtained at a solid content concentration of about 0.1% by weight or less.

  In addition, since polyfluoroalkylphosphonic acid or its salt has good solvent solubility, it easily forms a release agent solution having a uniform concentration, resulting in the precipitation that has been a problem with conventional release agents. And storage stability is also good.

Due to the various properties of the polyfluoroalkylphosphonic acid or its salt, the release agent according to the present invention has the following excellent effects.
(1) It has excellent film forming properties and can form a uniform coating film even on a molded product having a complicated shape.
(2) Excellent film forming property on the mold surface and adhesion to the mold surface by the ionic group, so that the mold release performance and the mold release life are remarkably improved.
(3) Excellent mold releasability and durability are exhibited even at a low concentration of about 0.1% by weight, so that mold contamination due to the mold release agent is reduced.
(4) Since the transferability of the release agent to the molded product is small, there is little adverse effect on the quality of the molded product after molding, and the dimensional accuracy of the molded product is improved.

Polyfluoroalkylphosphonic acid [I] has the general formula
_{C n F 2n + 1 (CH} 2 CF 2) a (CF 2 CF 2) b (CH 2 CH 2) c P (O) (OR) 2 (II)
(Where R is an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3) ) Represented by a hydrolysis reaction.

The polyfluoroalkylphosphonic acid diester [II] used as a raw material for this reaction is a polyfluoroalkyl iodide.
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b (CH ₂ CH ₂ ) _c I (III)
And trialkyl phosphite P (OR) ₃ . Polyfluoroalkyl iodide [III] is a known compound and is described in Patent Document 8.

Polyfluoroalkyl iodide [III] as a starting material for the synthesis of polyfluoroalkylphosphonic acid diester [II]
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b I (IV)
It is produced by addition reaction of ethylene with a terminal iodinated compound represented by the formula: The addition reaction of ethylene is carried out by subjecting the above compound [IV] to an addition reaction of pressurized ethylene in the presence of a peroxide initiator, and the number of addition depends on the reaction conditions, but is preferably 1 to 3, preferably 1. Although the reaction temperature is related to the decomposition temperature of the initiator used, the reaction is generally performed at about 80 to 120 ° C., and when a peroxide initiator that decomposes at a low temperature is used, the reaction temperature is 80 ° C. or less. Reaction is possible.

Peroxide initiators include tertiary butyl peroxide, di (tertiary butyl cyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diisopropyl Secondary butyl peroxydicarbonate or the like is used in a proportion of about 1 to 5 mol% with respect to the compound [IV] from the viewpoint of the progress and controllability of the reaction.

The terminal iodinated compound [IV] is synthesized through the following series of steps.
(1) General formula
C _n F _{2n + 1} I (n: 1-6)
Is reacted with vinylidene fluoride in the presence of a peroxide initiator as described above (amount used in an amount of about 0.1 to 0.5 mol% based on the raw material compound),
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a I (V)
To obtain a compound represented by:
(2) By reacting the compound represented by the general formula [V] with tetrafluoroethylene in the presence of a peroxide initiator, the terminal iodinated compound represented by the general formula [IV] is obtained. In the general formula [IV], b is an integer of 1 to 3, preferably 1 to 2. As the peroxide initiator used in this reaction, the organic peroxide initiator as described above is used in the same proportion as (1).

The reaction temperature of vinylidene fluoride and tetrafluoroethylene addition reaction also depends on the decomposition temperature of the initiator used, but by using a peroxide initiator that decomposes at low temperatures, Reaction is possible. In the reaction, when C _n F _{2n + 1} I or the compound [V] is put in an autoclave and the internal temperature is raised to about 10-60 ° C., for example, 50 ° C., C _n F _{2n + 1} is added thereto. Peroxide-based initiator dissolved in I or compound [V] is added, and when the internal temperature reaches 55 ° C., for example, vinylidene fluoride or tetrafluoroethylene is added while maintaining a pressure of about 0.1 to 0.6 MPa, After the desired amount is dispensed, it is carried out, for example, by aging at a temperature of about 55 to 80 ° C. for about 1 hour. The number a or b of vinylidene fluoride or tetrafluoroethylene skeleton added by the reaction depends on the amount added. Generally, it is formed as a mixture of various a and b values.

  The fact that these reactions can be carried out at low temperatures not only makes it possible to reduce the amount of energy used, but also suppresses corrosion due to hydrofluoric acid in the equipment and reduces the frequency of equipment renewal. Can do. Furthermore, since it is possible to use a cheaper material, it is possible to keep down the capital investment cost at a low price together with a decrease in the renewal frequency.

Specific compounds [IV] to which ethylene is added include the following compounds. These compounds are mixtures of oligomers having various a and b values, and oligomers having specific a and b values can be isolated by distilling the mixture. In addition, the oligomer which does not have predetermined | prescribed a value and b value can be used again for the oligomer number increase reaction with vinylidene fluoride or tetrafluoroethylene, isolating it or with a mixture.
C ₂ F ₅ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) I
C ₂ F ₅ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ I
C ₂ F ₅ (CH ₂ CF ₂ ) ₂ (CF ₂ CF ₂ ) I
C ₂ F ₅ (CH ₂ CF ₂ ) ₂ (CF ₂ CF ₂ ) ₂ I
C ₄ F ₉ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) I
C ₄ F ₉ (CH ₂ CF ₂ ) ₂ (CF ₂ CF ₂ ) I
C ₄ F ₉ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ I
C ₄ F ₉ (CH ₂ CF ₂ ) ₂ (CF ₂ CF ₂ ) ₂ I
C ₂ F ₅ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₃ I
C ₄ F ₉ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₃ I

Polyfluoroalkyl iodides [III] obtained by addition reaction of ethylene with compounds [IV] as exemplified above include trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite. By reacting trialkyl phosphite P (OR) ₃ having an alkyl group having 1 to 4 carbon atoms, such as de-RI, polyfluoroalkylphosphonic acid as a raw material of polyfluoroalkylphosphonic acid [I] Diester [II] can be obtained. In addition, unless the compound [IV] is subjected to an addition reaction with ethylene, the deRI reaction with the trialkyl phosphite does not proceed.

  The hydrolysis reaction of the polyfluoroalkylphosphonic acid diester [II] is easily performed by stirring at about 90 to 100 ° C. in the presence of an acidic catalyst such as an inorganic acid typified by concentrated hydrochloric acid. After the reaction mixture is filtered under reduced pressure, the target product polyfluoroalkylphosphonic acid [I] can be obtained in a good yield of 90% by a method such as washing with water, filtration, washing with acetone and filtration. .

The obtained polyfluoroalkylphosphonic acid can be neutralized and used in the form of a salt. The formation of the salt is generally confirmed by checking the equivalence point at pH, for example, sodium hydroxide, ammonium hydroxide, zinc sulfate, zinc acetate, zinc oxide, triethylamine, morpholine, triethanolamine, tris (2-hydroxy Titration with a salt-forming reagent such as ethyl) to obtain an acidic monovalent to trivalent metal salt, amine salt or ammonium salt. The polyfluoroalkyl phosphonates obtained, for example, sodium polyfluoroalkylphosphonic acid, potassium, lithium, barium, magnesium, calcium, metal salts such as zinc, ammonium salts, monoethyl, monoisopropyl, diethyl, dicyclohexyl, triethyl alkyl group or ammonium salts substituted with a cycloalkyl group, monoethanolamine, diethanol, triethanol ammonium salt substituted with a hydroxyalkyl group diisopropanolamine, etc., and the like.

The preparation of the release agent using polyfluoroalkylphosphonic acid or a salt thereof is an aqueous solution, aqueous dispersion or organic solvent solution having a solid content of about 0.01 to 30% by weight, preferably about 0.05 to 3% by weight. Is diluted with water or an organic solvent. The organic solvent used, methanol, ethanol, n- propanol, alcohols such as isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and the like, ethyl acetate, Esters such as butyl acetate, polyhydric alcohol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol and ethyl carbitol, carbon tetrachloride, methylene chloride, trichloroethylene, perchloroethylene, trichloroethane, trichlorofluoromethane, tetrachlorodifluoroethane , include at least one such halogenated hydrocarbons such as trichlorotrifluoroethane, preferably isopropanol and ethanol mixed The solvent is used. Here, the organic solvent can be used in combination with water.

In the release agent solution, if necessary, an amine-based neutralizer such as triethylamine, triethanolamine, tris (2-hydroxyethyl) amine, morpholine, an ionic or non-ionic agent that improves the wettability of the release agent. Various surfactants such as ionic type, silicone oil, silicone varnish and the like for further improving the releasability and lubricity can also be added.

The mold release agent solution can be applied to the mold by any commonly used method such as dipping, spraying, brushing, aerosol spraying, and application with an impregnated cloth. As the molding material mold release agent is formed in a mold which is coated, for example, polyurethane, polycarbonate, epoxy resin, phenol resin, polyimide resin, resins such as vinyl chloride resin, natural rubber, chloroprene rubber, fluorine rubber And rubbers.

  Next, the present invention will be described with reference to examples.

Example 1
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) I (99GC%)
500 g (0.78 mol) and triethyl phosphite P (OC ₂ H ₅ ) ₃ 181 g (1.56 mol) were charged and stirred at 155 ° C. At this time, ethyl iodide by-product in order to remove from the reaction system, a nitrogen gas was bubbled into the reaction solution using a small tube. A small amount of the reaction solution was collected and analyzed by gas chromatography. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added four times to 91 g (0.78 mol) at a time and stirred for a total of 18 hours. .

  After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C., and a tower top temperature of 150 to 155 ° C., and the distillation fraction was washed with water to obtain a purified reaction product (96 GC% ) 412 g (yield 78%) was obtained.

The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of ¹ H-NMR and ¹⁹ F-NMR.
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂

(2) In a four-necked flask thermometer and volume 1L equipped with a condenser, polyfluoroalkyl phosphonate diester obtained
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂ (96GC%)
300 g (0.44 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 276 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 242 g (0.41 mol, yield 92%) of the desired product.

From the results of ¹ H-NMR and ¹⁹ F-NMR, the obtained product was confirmed to be the target compound (polyfluoroalkylphosphonic acid) represented by the following formula.
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) P (O) (OH) ₂

(3) 5 parts by weight of the obtained polyfluoroalkylphosphonic acid was added to 93.5 parts by weight of ion-exchanged water and mixed, and 1.5 parts by weight of triethylamine was added thereto to carry out a neutralization reaction. A liquid was prepared. This mold release agent A was diluted 10 times with ion-exchanged water, and the mold release property and mold release life were evaluated by the following method using the obtained mold release agent solution. The latter was 12 times.
Mold releasability: 100 parts by weight of polyurethane prepolymer heated to 80 ° C. (Japan Polyurethane Industry product Coronate C-4090) and heat-melted methylene-bis- o -chloroaniline curing agent (Ihara Chemical product Iharacamine) (MT) 12.8 parts by weight were stirred and mixed while avoiding entrainment of bubbles, and this was poured into a mold made of spray-released aluminum sprayed with a release agent sprayed at 80 ° C with a diameter of 45 mm and a depth of 50 mm. In order to remove the cured molded product, pull the hook that has been set in advance in the middle of the mold space to remove the molded product from the mold. Measurement Mold release life: Repeated operation similar to that performed for mold releasability, and can be released up to several times with a release weight of 5kgf (49N) or less by applying a release agent once. Measure

Example 2
In Example 1 (3), when the mold release agent A was diluted 20 times with ion-exchanged water, the mold releasability was 10 N and the mold release life was 10 times.

Example 3
In Example 1 (3), when the mold release agent A was diluted 30 times with ion-exchanged water, the mold releasability was 15 N and the mold release life was 9 times.

Example 4
In Example 1 (3), a solution obtained by diluting the release agent A solution 40 times with ion-exchanged water was used. As a result, the mold releasability was 19 N and the release life was 7 times.

Example 5
In Example 1 (3), when the release agent A solution was prepared and diluted, a mixed solvent of isopropyl alcohol and isooctane-isopropyl alcohol (weight ratio 90:10) was used instead of ion-exchanged water. The mold releasability was 7N and the mold release life was 11 times.

Example 6
5 parts by weight of the polyfluoroalkylphosphonic acid obtained in Example 1 (2) was added to and mixed with 78.5 parts by weight of ion-exchanged water and 15 parts by weight of ethanol, and 1.5 parts by weight of morpholine was added thereto. A summing reaction was performed to prepare a release agent B solution. This release agent B solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 9N and the latter was 10 times.

Example 7
5 parts by weight of the polyfluoroalkylphosphonic acid obtained in Example 1 (2) was added to and mixed with 78.5 parts by weight of ion-exchanged water, 12 parts by weight of ethanol and 3 parts by weight of isopropanol, and 1.5 parts by weight of triethylamine was added thereto. Was added to perform a neutralization reaction to prepare a release agent C solution. This release agent C solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 8N and the latter was 10 times.

Example 8
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) I (99GC%)
500 g (0.92 mol) and triethyl phosphite P (OC ₂ H ₅ ) ₃ 213 g (1.84 mol) were charged and stirred at 155 ° C. At this time, ethyl iodide by-product in order to remove from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary. A small amount of the reaction solution was collected and subjected to gas chromatography analysis. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added 4 times to 107 g (0.92 mol) at a time and stirred for a total of 18 hours. .

  After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 145 to 155 ° C., and a tower top temperature of 138 to 142 ° C., and the distillation fraction was washed with water to give a purified reaction product (98 GC% 407 g (79% yield) was obtained.

The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of ¹ H-NMR and ¹⁹ F-NMR.
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂

(2) In a four-necked flask thermometer and volume 1L equipped with a condenser, polyfluoroalkyl phosphonate diester obtained
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂ (96GC%)
300 g (0.53 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover 287 g of a solid content. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 240 g (0.49 mol, yield 93%) of the desired product.

From the results of ¹ H-NMR and ¹⁹ F-NMR, the obtained product was confirmed to be the target compound (polyfluoroalkylphosphonic acid) represented by the following formula.
CF ₃ (CF ₂ ) ₃ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) P (O) (OH) ₂

  (3) Using 5 parts by weight of the obtained polyfluoroalkylphosphonic acid, the same reaction as in Example 7 (3) was performed to prepare a mold release agent D solution. This release agent D solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 14N and the latter was 9 times.

Example 9
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₃ (CH ₂ CH ₂ ) I (97GC%)
500 g (0.76 mol) and triethyl phosphite P (OC ₂ H ₅ ) ₃ 176 g (1.52 mol) were charged and stirred at 155 ° C. At this time, ethyl iodide by-product in order to remove from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary. A small amount of the reaction solution was collected and subjected to gas chromatography analysis. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added to 88 g (0.76 mol) at a time, and stirred for a total of 18 hours. .

  After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C., and a tower top temperature of 150 to 155 ° C., and the distillation fraction was washed with water to obtain a purified reaction product (96 GC% ) 395 g (yield 77%) was obtained.

The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of ¹ H-NMR and ¹⁹ F-NMR.
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₃ (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂

(2) In a four-necked flask thermometer and volume 1L equipped with a condenser, polyfluoroalkyl phosphonate diester obtained
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₃ (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂ (96GC%)
300 g (0.44 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 276 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 237 g (0.40 mol, yield 90%) of the desired product.

The resulting product, the results of ¹ H-NMR and ¹⁹ F-NMR, it was confirmed that the target compound represented by the following formula (polyfluoroalkyl phosphonic acid).
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₃ (CH ₂ CH ₂ ) P (O) (OH) ₂

  (3) Using 5 parts by weight of the obtained polyfluoroalkylphosphonic acid, the same reaction as in Example 7 (3) was performed to prepare a release agent E solution. This release agent E solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 11N and the latter was 8 times.

Example 10
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) I (97GC%)
500 g (0.90 mol) and triethyl phosphite P (OC ₂ H ₅ ) ₃ 208 g (1.80 mol) were charged and stirred at 155 ° C. At this time, ethyl iodide by-product in order to remove from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary. A small amount of the reaction solution was collected and analyzed by gas chromatography. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added 4 times to 104 g (0.90 mol) at a time and stirred for a total of 18 hours. .

  After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 145 to 155 ° C., and a tower top temperature of 138 to 141 ° C., and the distillation fraction was washed with water to give a purified reaction product (97 GC% ) 397 g (yield 78%) was obtained.

The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of ¹ H-NMR and ¹⁹ F-NMR.
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂

(2) In a four-necked flask thermometer and volume 1L equipped with a condenser, polyfluoroalkyl phosphonate diester obtained
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂ (95GC%)
300 g (0.52 mol) and 300 g of about 35% concentrated hydrochloric acid were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 271 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 235 g (0.48 mol, yield 92%) of the desired product.

From the results of ¹ H-NMR and ¹⁹ F-NMR, the obtained product was confirmed to be the target compound (polyfluoroalkylphosphonic acid) represented by the following formula.
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) P (O) (OH) ₂

  (3) Using 5 parts by weight of the obtained polyfluoroalkylphosphonic acid, the same reaction as in Example 7 (3) was performed to prepare a release agent F solution. This release agent F solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent F solution. As a result, the former was 12N and the latter was 8 times.

Example 11
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) ₂ I (97GC%)
500 g (0.88 mol) and triethyl phosphite P (OC ₂ H ₅ ) ₃ 204 g (1.76 mol) were charged and stirred at 155 ° C. At this time, ethyl iodide by-product in order to remove from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary. A small amount of the reaction solution was collected and analyzed by gas chromatography. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added 4 times to 104 g (0.90 mol) at a time and stirred for a total of 18 hours. .

  After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 145 to 155 ° C., and a tower top temperature of 140 to 142 ° C., and the distillation fraction was washed with water to give a purified reaction product (97 GC% 410 g (79% yield).

The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of ¹ H-NMR and ¹⁹ F-NMR.
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) ₂ P (O) (OCH ₂ CH ₃ ) ₂

(2) In a four-necked flask thermometer and volume 1L equipped with a condenser, polyfluoroalkyl phosphonate diester obtained
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) ₂ P (O) (OCH ₂ CH ₃ ) ₂ (97GC%)
300 g (0.51 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 269 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 240 g (0.46 mol, yield 90%) of the desired product.

From the results of ¹ H-NMR and ¹⁹ F-NMR, the obtained product was confirmed to be the target compound (polyfluoroalkylphosphonic acid) represented by the following formula.
_{CF 3 (CF 2) (CH} 2 CF 2) (CF 2 CF 2) 2 (CH 2 CH 2) 2 P (O) (OH) 2

  (3) Using 5 parts by weight of the obtained polyfluoroalkylphosphonic acid, the same reaction as in Example 7 (3) was performed to prepare a release agent G solution. This release agent G solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 12N and the latter was 8 times.

Example 12
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) I (98GC%)
500 g (1.12 mol) and triethyl phosphite P (OC ₂ H ₅ ) ₃ 259 g (2.24 mol) were charged and stirred at 155 ° C. At this time, ethyl iodide by-product in order to remove from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary. A small amount of the reaction solution was collected and subjected to gas chromatography analysis. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added four times to 130 g (1.12 mol) at a time and stirred for a total of 18 hours. .

  After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 130 to 140 ° C., and a tower top temperature of 128 to 131 ° C., and the distillation fraction was washed with water to obtain a purified reaction product (98 GC% ) 405 g (yield 79%) was obtained.

The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of ¹ H-NMR and ¹⁹ F-NMR.
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂

(2) In a four-necked flask thermometer and volume 1L equipped with a condenser, polyfluoroalkyl phosphonate diester obtained
CF ₃ (CF ₂ ) (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) (CH ₂ CH ₂ ) P (O) (OCH ₂ CH ₃ ) ₂ (94GC%)
300 g (0.63 mol) and 300 g of about 35% concentrated hydrochloric acid were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 262 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 229 g (0.59 mol, yield 93%) of the desired product.

From the results of ¹ H-NMR and ¹⁹ F-NMR, the obtained product was confirmed to be the target compound (polyfluoroalkylphosphonic acid) represented by the following formula.
_{CF 3 (CF 2) (CH} 2 CF 2) (CF 2 CF 2) (CH 2 CH 2) P (O) (OH) 2

  (3) Using 5 parts by weight of the obtained polyfluoroalkylphosphonic acid, a reaction was carried out in the same manner as in Example 7 (3) to prepare a release agent H solution. This release agent H solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 14N and the latter was 7 times.

Reference example
Using 5 parts by weight of a polyfluoroalkylphosphonic acid having a perfluoroalkyl group having 8 or more carbon atoms represented by CF ₃ (CF ₂ ) ₇ (CH ₂ CH ₂ ) P (O) (OH) ₂ , Example 7 ( Reaction was carried out in the same manner as in 3) to prepare a release agent I solution. This release agent I solution was diluted 20 times with ion-exchanged water, and the mold release property and release life were evaluated in the same manner as in Example 1 (3) using the obtained release agent solution. However, the former was 13N and the latter was 5 times.

Comparative Example In Example 1, the mold releasability and the release life were evaluated without using a release agent. However, the former was not able to be measured because the molded product was not peeled off from the mold, so the release life was also low. The result was 0 times.

Claims (6)

General formula
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b (CH ₂ CH ₂ ) _c P (O) (OH) ₂ (I)
Wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3, or a salt thereof. Release agent as an active ingredient.   The mold release agent according to claim 2, which is used as an aqueous solution.   The mold release agent according to claim 2, which is used as an aqueous dispersion.   The mold release agent according to claim 2, which is used as an organic solvent solution.   The mold release agent according to claim 1, 2 or 3, wherein the polyfluoroalkylphosphonic acid or a salt thereof has a solid concentration of about 0.01 to 30% by weight.   The mold release agent according to any one of claims 1 to 5, which is used by being applied to a molding die.