JPS588757A - Release agent - Google Patents

Abstract

PURPOSE:To provide a release agent exhibiting excellent releasability with a small amount of application to the surface of a mold, prepared by adding at least one of silicone oil, silicone varnish, wax and fluorinated organic compd. to a specified fluorine-contg. polyester copolymer. CONSTITUTION:The release agent is prepared by adding at least one of silicone oil, silicone varnish, wax and highly fluorinated organic compd. with a b.p. of 100 deg.C or higher (e.g., perfluorobutyltetrahydrofuran) to a fluorine-contg. polyester copolymer having structural units of formulaIor II (where Rf is 3-21C perfluoroalkyl; n is 0-1), formula III (where R is a residual group obtained by removing formula IV from a cyclic acid anhydride) and, when necessary, formula V (where R1-4 are H, alkyl or aryl) and/or VI (where R5 is H, alkyl or aryl; m is 2-3).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mold release agent, more specifically a synthetic Vji fat or jΔ(
The present invention relates to a mold release agent used in the production of molded products such as polymer materials such as synthetic resins (hereinafter referred to as synthetic resins and composites, and foams thereof), cement, and 13 lamic.

Conventionally, for example, natural or synthetic compounds such as silicone oil, mineral oil, paraffin wax, fatty acid derivatives, tariol, etc., and inorganic substances such as talc 5 mica, etc., have been used for molding polymer materials, cement, etc. It is used as an r4 type agent. Generally, these mold release agents are applied to the mold before the object to be molded is introduced, and if the mold release life is short, it is usually applied before each introduction. Silicodioil is the most widely used mold release agent because of its good mold release properties, but even in this case, when used for strong adhesive materials such as urethane and epoxy resin, it is difficult to oxidize. It is necessary to improve the strength of the release agent film by adding fine silicon powder or the like, and to apply it in large quantities.

Applying such a large amount causes the release agent to migrate to the molded object, which not only makes it impossible to perform post-treatments on the surface of the molded object, such as painting or adhesive treatment, but is also undesirable from a cost perspective. That's not the point.

Furthermore, by applying a large amount of mold release agent (i-), if you continue molding with one mold, mold release agent residue and molded product residue will accumulate on the mold surface, making it necessary to wash the mold frequently. This caused a decrease in the efficiency of the molding process.

Fluorine compounds have a low surface energy of 141 tons! Is it known that you have a barfluo Q? A mold release agent with good mold release properties has been obtained by blending silicic acid ester of alcohol having an L+L group with silico oil, etc. (Japanese Patent Publication No. 53-2327
1).

However, a mold release agent containing a phosphate ester of an alcohol having a perfluoroalkyl group is difficult to use because the phosphate ester has a reactive performance (for example, polyurethane foam has a moderately reactive M'fe). During the resin molding process, some parts may react with the resin surface, causing the surface to become rough.In the case of molds, the mold releasability is very good, but
In the case of plastic molds such as the epoxy type, there is a drawback that the mold releasability is somewhat poor, probably because the orientation of the perfluoroalkyl groups is not good.

51 The present inventors have conducted extensive research in order to eliminate the drawbacks of the conventional mold release agents mentioned above, and have found that silicone oil, silicone varnish, wax, etc. and boiling point! By blending at least one type of highly fluorinated organic compound with a temperature of 00°C or higher, the molded product has good releasability from the mold, and the surface properties of the molded product are also improved. We have discovered a mold release agent that exhibits excellent mold release properties even in resin molds.

That is, the present invention provides (a) a fluorine-containing polyester copolymer 6- having the following structural unit [wherein Rf is a perfluoro-al+ group having 3 to 21 carbon atoms, and n is an integer of 0 or 1] . ] and shows the remaining funds after excluding O O. ] and as necessary (c) 40CR□R2CR3R4-) [However, R
R4 to R4 each represent a hydrogen atom, an alkyl group or an alkyl group containing a substituent, or an aryl group or an aryl group having a substituent. ] 7- and/or [N<CH2), -3 Yabutsuji-85 [However, R5 represents a hydrogen atom, an alkyl group or an aryl group, and m represents an integer of 2 or 3. and (Ii) a mold release agent containing at least one of silicone oil, silicone varnish, wax, and a highly fluorinated organic compound with a boiling point of +00'C or higher.

The mold release agent of the present invention is extremely effective when applied in a small amount to the mold surface.
Since it exhibits E-type properties, the surface of the molded product does not become sticky or the surface of the pattern becomes dirty.

The fluorine-containing copolymer used in the present invention is a known one, such as JP-A-53-139696 or JP-A-53-13.
9697.

8- That is, between the copolymers of the present invention, (a') is an epocytosite represented by the formula: (Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, and n is an integer of 0 or 1); Cyclic acid anhydride represented by the formula (b'): (% formula % represents a group) and optionally the formula (C'): (R□ to R4 are each a hydrogen atom, an alkyl group, or an alkyl group having a substituent. (represents an aryl group, an aryl group, or an aryl group having a substituent) and/or R, C, -0 (R5 is a hydrogen atom, an aryl group, or an aryl group; (denoting an integer of ) under polymerization conditions.

Cyto(a)) is a known compound. For example, 2-barfluo0al+ru1,2-evo+sietashi (pt=o
case) is described in German Patent Application No. 21 60 783. Also, 3-barfluo 0 al + ru 1
．． 2-Evo 10 Shibu 0 Pan (in the case of n-1) is
It is described in the specification of Japanese Patent Application No. 4-26286, and can be produced by the reaction of 3-valuroroal-2-iodopanol-1 and alkali hydroxide.

Here, the perfluoroalkyl group has 3 to 21 carbon atoms, particularly preferably 5 to 16 carbon atoms. It is also possible to use a mixture of two or more types of epocites having different numbers of carbon atoms in the barfluoroal+ru group as the raw material.

The cyclic acid anhydride (b'), which is another raw material, is
two carbon atoms (carbo+ with single or double bonds to each other)
A five-membered ring compound dehydrated from a syl group, examples of which include succinic anhydride, maleic anhydride, phthalic anhydride, diomellitic anhydride, and 1,2-Schiffyl dicarboxylic acid. Anhydride, tetradolphthalic anhydride, 1
, 2,3,4-Schiff0pecitanetetracarboxylic acid dianhydride, l,2-cyclobutane dicarboxylic acid anhydride, nizidic anhydride, 1,2-natutale dicarboxylic acid anhydride, 2,3-natutale dicarboxylic acid anhydride Examples include acid anhydrides and substituted products thereof.

In addition, the epoxy compounds (C'-1") include ethylene + cyto, diurene + cyto, isoptylene + cyto, butadiene + cyto, styrene + cyto, and engineering 0.
Examples include engineered halogenated phosphorus such as halogenated hydrine, alkyl or aryl talicidyl ether such as methyl cricidyl ether and phenyl cricidyl ether.

Another raw material, cyclic imino ether (t'-2
Examples of ``) include 2-o++j lysine, 5,6-dishido 4H-1,3-1delysine, and substituted derivatives thereof.

In the copolymer (2) according to the present invention, the content of (a) is preferably 30 to 70 tl%. 3O-EJL,%
If the amount is less than 1, the release property will be poor and a large amount will be required in the composition, which may interfere with the properties of ω). When it is more than 70V nil%, the prison substance and I
B) It is not preferable because the affinity with the substance decreases.

- (b) and (C) are therefore preferably 30 to 70 t1% chi.

Next, the silicone oil used in the present invention is liquid or solid at room temperature, has a boiling point of 100°C or more, and has a melting point of 1.
Non-curing polysiloxanes at 50°C or less are preferably those having an alkyl group, a fluoroal+yl group, a phenyl group, etc. in the side chain, and more preferably those having a high methyl group content. Worth it.

As the silicone varnish used in the present invention, a wide variety of known silicone varnishes can be used, such as methyl silicone varnish. Methyl silicone varnish is S
It is a copolymer consisting of various combinations of structural units of iO2, CH35iO1(CH3)2% 5iO1(CH3)3SiO1/, and has a three-dimensional network structure. The copolymer may or may not have a crosslinkable group (eg, hydroxyl group, etc.).

Among such methyl silicone varnishes, those soluble in organic solvents are particularly preferred.

In addition, a highly fluorinated organic compound (hereinafter abbreviated as a high fluorine compound) refers to a compound in which atoms that can be fluorinated and have a boiling point of 100° C. or higher are highly fluorinated.

Examples of such compounds include H(CF2CF2)nC
F2, [(CF3)2CF(CF2)n]2, C1(C
F2CF2) Highly fluorinated alkyl compounds such as #CHF2, fluorinated compounds such as hexafluoromer, and derivatives thereof, F (-C
F(CF3)CF20]nCHFCF3(C4F9)
Examples include highly fluorinated amines such as 3N, more specifically (CF3)2CF(CF2).
4CF (CF3) 2b door 207°CS CF3 (CF2
)4CC13bp143°OS CICCF2CFCl
>3C66 units 2 0 3°C1C2F5CFCICF
2CFC126 units 119°c1 C9F2ob units 1
25°C, C9HF1. bl' I 3 8°c
, CF2C1(CF2)5CHF2 b door 123℃,
cHF2 (CF2) 7cF2cl 6 units 162°C
1C11HC”22 bp 1 9 1 °cS
CF3(CF2)2CF(CF2)4CF2b door 225
To °C1+Safluo Dpu0hentrimmer bpI 10~
114°C1 Tetrafluoroethylene Pentamer 6 units 130~1″32°C, Barfluoroethylene Pentamer Ap
142°C, barfluorobutyltetrahyde 0 Furan Pass 102°C1FCCF(CF3)CF20〕4CHF
CF3b door 193°C1 (C4F9) 3N pass +74°C
etc. can be exemplified. Most of these are liquid at room temperature, but some are solid. Melting point is 150
below °C. Next, the waxes used in the present invention include not only animal and vegetable waxes that have been used for a long time, but also mineral or synthetic waxes such as rosefish wax, and are waxes in a broad sense. Specific examples of such waxes include vegetable waxes made of fatty acid esters such as carnauba wax and candela wax, mineral waxes such as polyethylene wax, micro wax, and FT wax, wool wax, and vegetable waxes such as Mitsu-09. can be mentioned. Secondary waxes can also be used alone or in combination of two or more.

In the present invention, the ratio of the above barfluoroalkyl group-containing polyester to at least one of silicodioyl, silicosi varnish, wax, and highly fluorinated fluorine compound having a boiling point of 100°C or higher is preferably 1:0.1 to 10. is preferably 1:0.3 to 5.

In the present invention, various surfactants such as cationic, anionic, and nonionic surfactants may be used as necessary to improve the stability and wettability of the mold release agent, and also to improve mold release properties and lubricity. For the purpose of improvement, fluororesin powder, fluoride carposi, aluminum powder, copper powder, mica powder, and mica may be added.

The composition of the present invention is generally used for mold release by dissolving or dispersing it in an organic solvent or an aqueous medium. Examples of organic solvents that can be used include alcohols such as methanol, ethanol, dipanol, and isopropanol, ketones such as acetate, methyl ethyl ketone, and methyl isobutyl ketone, ethyl ether, isoproyl ether, diosaccharide, and tetrahydrocarbon. Ethers such as furan, ethyl acetate,
Esters such as butyl acetate, hydrocarbons such as tornidi and tenshireshi, carbon tetrachloride, methylene chloride, ethylene chloride,
Examples include halogenated hydrocarbons such as trichlorethylene, bicarbonate ethylene, trichloroethane, trifluoromethane, trifluoroethylene, and trifluorotrifluoroethane. The secondary organic solvents can be used alone or in combination.

An example of the method for preparing the composition of the present invention is shown below.

First, when obtaining an organic solvent-based mold release composition, a polyester containing a barfluoro-al+ru group is dissolved in trifluoro-trifluoro-ethane, etc., and silicone oil, silicone varnish wax, etc. are dissolved in tonorenine, decalyne, etc. Simply add the solution and mix both solutions. In addition, in order to obtain an aqueous mold release composition, a perfluoro alkyl group-containing polyester is fractionally emulsified in water using a cationic, anionic, or nonionic surfactant, and then When applying the mold release composition of the present invention to a mold, the concentration of the mold release composition may be determined by mixing emulsified silicone oil or the like in the same manner as above. The total amount of active ingredients in the medium is generally 0.
The amount is preferably 1 to 50% by weight, but depending on the purpose of the mold release composition, for example, if the purpose is only one-time mold release, 0.1% by weight or less is usually sufficient. When applying a mold release composition to require a particularly long service life, it is usually appropriate to use 0.5 to 20% by weight, preferably 1 to 10% by weight.

Examples of raw materials for molded products to be released from the mold in the present invention include polyurethane, chlorobrasion rubber, polycarbonate, fluorine resin, epoxy resin, phenol resin,
Synthetic stakes such as vinyl chloride resin [fat or synthetic rubber, appropriate natural resins or natural rubbers, etc. are mentioned, and particularly when applied to foamed polyurethane [phthalate, etc.], good mold releasability is shown.

Generally known methods may be used to apply the mold release composition of the present invention to a mold, such as by dipping the mold in the mold release composition, spraying, brushing, etc., or by soaking it into cloth. It can be applied by smearing and the medium can be removed by evaporation.

Depending on the object to be released, it may not be necessary to evaporate the medium, but when molding urethane resin, etc., it must be completely removed by evaporation.

Experimental examples are shown below to make the features of the present invention clearer.

<Experimental Example 1> 1 Purpose: Various mold release agents were subjected to a mold release test for hard tan foam and a mold release test for epoxy resin, and their mold release properties were measured.

2. Release agent used: Fluorine-containing polyester copolymer Five types of copolymers shown in Table 1 were used.

Table 1 When the fluorine-containing polyester shown in Table 1 is used as a solution-type mold release agent, it is used after being dissolved in a solvent such as 1-1-2-1-lifluorotrichloroethane.

In addition, when using it as an aqueous mold release agent, dissolve 10 parts of the copolymer prepared in Table 1 in 15 parts of methyl isobutyl ketone, and add Nonion H5240 (Nonion H5240 (manufactured by NOF Corporation)). Activator) 0.2 parts, Nymeen 52
15C Nonionic surfactant manufactured by Nippon Oil & Fats Co., Ltd.) 0.
4 parts and 74° of water and 3
Stir at high speed for 0 minutes to make a milky white aqueous emulsion, then dilute with water and use.

In Table 1, CI] and (n) respectively indicate the following.

However, the composition of n) is 557% for m=3, 28'e To% for m1=4, 111:1% for m=5, m=
6 is 4 U%, m = 7 is l E To % te.

(Ex) Substances used in combination with the above copolymer The substances listed above and u3) are shown in Table 2 for the mold release test of hard horsetail foam, and in Table m3 for the mold release test of epoxy resin. They were mixed in the predetermined ratio shown to form a mold release agent.

3 Mold release test of hard uretashi foam: (A) Composition of hard uretashi foam 1-liquid A PPG-5U, -45 (
: JL 100 parts (polyol manufactured by Mitsui Tosho ■) CC43F (foaming agent) 44 parts triethylenecidiamine 0.3 parts N, ■-dimethane 1, ethanol, amine 1.5s L-53201, 5 parts B solution 4, 4'-diphenyl meta, 1 115.4
Part diisocyanate 1.
The mixture was stirred and mixed at 0 rpm, immediately poured onto the aluminum plate, and foamed and hardened at 25°C. After standing for 30 minutes, the mold release performance is measured by 90° peel strength using a tensile tester (tensile speed: 20,011 st/min). The mold release life is determined by applying the mold release agent once and continuing without further application until the mold releasability deteriorates. That is, the molding life is defined as the number of molded products that can be removed in perfect shape by repeating molding without applying a mold release agent. The mold releasability values in Table 2 are the average judgment values of mold releasability when measured in this manner.

4 S-type test of Epo+Si resin: Composition A of Epo+Si resin Engineering coat $828 (made by Shell Chemical) 100 parts B
Liquid triethylenetetra Enia 10 parts...)
Test Method 103X A mold release agent is brushed onto a 103 aluminum mold and air dried. Next, the epoxy resin and the above A and B solutions were thoroughly mixed, impregnated with 10cIIIX 10 [(7)tj last coat [Chop Stracid Mat Nitto Boseki ■], and then poured into a mold.

After being left to cure at 25°C for one day, it was tested at 90° using a tensile tester (tensile speed 200MM/min).
Mold release performance is measured by peel strength.

The mold release life is determined by applying a mold release agent once and then continuing without further application until the mold releasability deteriorates. That is, +31+ The molded product can be taken out in a perfect shape.The mold release life is defined as the number of molded products that can be taken out in a perfect shape by repeating molding without applying a release agent.

The mold releasability values in Table 3 are the most average judgment values for type IIi properties when measured in this manner.

C) Test results +36- <Experimental Example 2> 1 Purpose: Compare the mold release properties of a conventional mold release agent containing a phosphate ester of an alcohol containing a barfluoroal+ group and the mold release agent of the present invention. Tested.

2 Mold release agent used Mold release agent 1 CF3CF2 (CF2CF2)3CH2CH20PO (
OH) 21 parts dimethylsilo + sashio oil (350Cf)
1 ml 1-1-2-trifluorotrichloromethane 98 parts Mold release agent 2 Type 4 (Table 1) fluorine-containing polyester 1 part Dimethyl di-oil (350Cj) 1 ml
-1-2-) Refluor Oori D Lueta'J 98 parts 3 Mold release test (3) Composition of uretashi resin used Liquid A mlllionate MR-200 110 parts (
Nippon Polyurethane ■) B liquid m1llit) natz M -I Q I
QQ Section (Japan Polyurethane ■) Test method 10 A mold release composition was applied to the CIRXIQcI11 aluminum mold and epoxy resin mold with a brush and air-dried. 7 Next, stir and mix liquid A and liquid B, and immediately pour into the mold 45.
Cure for 20 minutes at °C.

Immediately after hardening, use a tensile tester (tensile speed 200 h/m1n).
), and the mold release performance is measured by 90° peel strength.

The mold release life is determined by applying the mold release agent once and continuing without further application until the mold releasability deteriorates.

That is, the molding life is defined as the number of molded products that can be taken out in a perfect shape by repeating molding without applying the interstitial agent. The mold releasability values in Table 4 are the average judgment values of the mold releasability when measured in this manner.

Table 4 Procedural amendment (see) 1. Indication of the case 1982 Patent Application No. 108025 2. Name of the invention Mold release agent 3. Person making the amendment Relationship with the case Patent applicant (2a5) Thailand + Shi Kogyo Co., Ltd. 4, Agent, Heiwa Building, 2-10 Hirano-cho, Higashi-ku, Osaka Telephone: 06-203
-0941 (Government) Sponsorship 6. Number of inventions increased by amendment. Contents of amendment 1. Deleting "or cement, ceramic, etc. J" from page 8, lines 6-7 of the specification.

2. Page 5 of the specification, lines 11-15 “The surface...
There are drawbacks. ``The disadvantage is that the surface may become rough. 1 and corrected.

8. On page 6 of the specification, line 6 [at least one kind or more] should be corrected to "at least one kind."

4. Page 8, line 7 of the specification [at least one or more 1 is corrected to ``at least one''.

5. The phrase [Silicon varnish used in the present invention] on page 14, line 8 of the specification is corrected to read [Silicon varnish 1 used in the present invention].

6. In the specification, page 14, lines 9-10, the phrase "methyl silicone varnish" is corrected to "methyl silicone varnish, etc.".

7. Page 14 of the specification, lines 10-11, “Methyl silicone varnish is” is replaced with “Methyl silicone varnish is,”
” he corrected.

8. The text "(hereinafter abbreviated as high fluorine compound)" on page 15, lines 8 to 4 of the specification is deleted.

9. Specification page 15, line 6 [H(OF20F2)n
OFi I is replaced with “H(OF20F2)n OF
Correct it as s J.

10. On page 17 of the specification, line 8, ``Plant-based'' is corrected to ``Animal-based.''

11. On page 17, line 12 of the specification, "in the present invention" is corrected to "in the present invention."

12. The phrase "highly fluorinated compound" on page 17, lines 14 to 16 of the specification is corrected to read "highly fluorinated organic compound with a boiling point of 100° C. or higher."

18. The statement ``Mica gold'' in line 8 of No. 18 of the specification is corrected to ``J for mica etc.''

14. On page 19 of the specification, line 14, "silicone varnish wax" is corrected to "silicone varnish, wax".

15. Specification, page 21, lines 7-8 [... is listed...shown]. ] Correct Toru as follows. [・
...is mentioned. In the case of foamed polyurethane, when conventional mold release agents are used, the reactive incyanate groups react with the functional groups in the mold release agent, often resulting in poor mold release properties or rough mold release surfaces. In the case of the present mold release agent, as can be seen from the synthesis method, the functional group 1 that reacts with the incyanate group is removed by a 6-caulking reaction, so there is no such inconvenience. ] 16, page 28, line 1 from the bottom of the specification to page 24, line 1 rl
-1-2-)Rifluorotrichloroethane" should be corrected to "r1.1.2-)Rifluorotrichloroethane."

17. In line 4 of No. 26a of the specification, the statement ``...was used as an fIAW agent.'' is corrected as follows. [...used as a mold release agent.

As a comparative example, cases of (g) or @ alone are also shown in Tables 2 and 8. 1 18, page 28 of the specification, bottom 12 line rL-5820J [L-5820 (foam stabilizer) (Nippon Unitika II)
Correct it with J.

19. In the first line from the bottom of the specification @26, the phrase "on an aluminum mold" is corrected to "on an aluminum mold."

20. On page 27 of the specification, line 8, ``On an aluminum plate'' is corrected to ``On an aluminum mold.''

21, Specification, page 27, lines 11-12 [Measured in this way...] ” is the average value of 8 measurements taken in this way. Correct it as 1.

22, in Table 2 described on pages 28 to 81 of the specification, the column for Comparative Example 1 and the column for Example 7 in the column of solvent or dispersion medium, "rl-1-1-trichloroethane" are respectively replaced by rl. , 1.1-trichloroethane".

28, Table 2 described on pages 28 to 81 of the specification, column of Comparative Example 10 in the section of solvent or dispersion medium [l-1-1
-) lichloroethane” should be corrected to “Ill, 1-trichloroethane.”

24. In Table 2 described on pages 28 to 81 of the specification, the column for Comparative Example 2, the column for Comparative Example 7, the column for Example 1, the column for Example 4, and the Examples in the section of solvent or dispersion medium. In column 6 and column r of Example 8, "1-1-2-trifluorotrichloroethane" is corrected to "1,1,2-trifluorotrichloroethane."

26. On page 82 of the specification, line 6, "aluminum mold top" is corrected to read "aluminum bottom mold top".

26. On page 82 of the specification, lines 10-11, the statement ``The product is impregnated with... and then poured into a mold at room temperature of 26°C...'' is corrected as follows. [After being impregnated with..., place it on the lower mold, then place the upper mold and press it down at room temperature of 25°C...1 27, Specification, page 88, lines 4-6 "Measuring in this way...
It is. ” is the average value of 8 measurements taken in this way. ” he corrected.

28, "art-t-t-trichloroethane" in the column of Comparative Example 1, the column of Comparative Example 10, and the column of Actual Example 7 in Table 8 on pages 84 to 87 of the specification in the column of solvent or dispersion medium.
Correct them to [t, t, t-trichloroethane].

29. In Table 8 described on pages 84 to 87 of the specification, the column for Comparative Example 2, the column for Comparative Example 7, the column for Example 1, the column for Example 4, and the Examples in the column of solvent or dispersion medium. In column 5, column of Example 6, and column of Example 8, the statement ``[t-1-2-)trifluorotrichloroethane'' is corrected to read ``t,t,2-trifluorotrichloroethane''.

80, page 38, line 10 of the specification rl-1-2-)
Trifluorotrichloroethane” is corrected.

81, page 88, line 14 of the specification [1-1-2-trifluorochloroethane] i is corrected as 1.L2-trifluorotrichloroethane 1.

82, details! Page 40, lines 4-5 [Measure in this way...
It is. 1 is the average value of 8 measurements. ] Corrected.

(that's all)

Claims (1)

[Scope of Claims] (a) A fluorine-containing polyester copolymer having the following structural units [wherein Rf is a tl-fluoroalkyl group having 3 to 21 carbon atoms, and n is an integer of O or 1] show. ] and 1-0 indicate the removed residues. ] and if necessary (ζ) + 0CRIR2CR3R4 [However, R
□ to R4 each represent a hydrogen atom, an alkyl group, an al+al group having a substituent, an aryl group, or an aryl group having a substituent, ]0<-R. [However, R5 represents a hydrogen atom, an aryl group, or an aryl group, and Misaki represents an integer of 2 or 3. ] and iH) A mold release agent comprising at least one of silicodioil, silicoci varnish, wax, and a highly fluorinated organic compound having a boiling point of 100° C. or more.