JPH0689149B2 - Method for producing fluorine-containing silicone-modified novolac resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a low water absorption novolak resin in which a fluorine-containing organopolysiloxane is introduced into a novolak resin.

Conventional techniques and problems to be solved by the invention Epoxy resins and epoxy resin compositions in which an inorganic filler is added to the epoxy resins generally have better moldability, adhesiveness, electrical properties, mechanical properties, and other properties than other thermosetting resins. Since it has excellent moisture resistance and the like, it has been widely used as various molding materials, powder coating materials, electrical insulating materials, and the like, and in recent years, it has attracted attention as a semiconductor sealing material.

However, many conventional epoxy resin compositions are cracked during curing, which impairs the appearance of the molded and painted surfaces and causes defects in devices and devices such as semiconductors. Therefore, in order to solve this problem, the present inventors previously added a block copolymer composed of an aromatic polymer and an organopolysiloxane to a curable epoxy resin to improve the crack resistance. An excellent epoxy resin composition has been proposed (JP-A-58-21417), but it is further excellent in crack resistance, has a high glass transition point, has a low expansion coefficient, and therefore has a small amount of deformation during molding. There is a demand for an epoxy resin composition which has excellent moldability and does not impair properties such as mechanical strength such as bending strength and bending elastic modulus.

Further, in recent years, in a molded product having a thin package structure, there has been a problem that the element and the molded product are cracked when immersed in a solder bath. The problem is
Although it is related to the increase of water absorption and internal stress of the package, this has not been satisfactorily improved. Therefore, development of an effective improvement method is desired.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a fluorine-containing silicone-modified novolac resin having low water absorption, which is preferably used as an additive for an epoxy resin composition.

Means and Actions for Solving the Problems The present inventors have blended an epoxy resin composition containing a curable epoxy resin and a curing agent as main components to achieve the above object, and have low water absorption and crack resistance. As a result of diligent study on the block copolymer component which brings about excellent curing, novolak resin and the following formula (1) [Wherein R ¹ is, an alkyl group or a phenyl group having 1 to 8 carbon atoms, each R ¹ may be the one another be the same or different, R ²
Is at least one selected from the group consisting of hydrogen atom or a monovalent organic group having an amino group, an epoxy group, a hydroxy group or an alkoxy group, and Rf is _{C m F 2m + 1 CH 2} CH 2 OCH 2 CH 2 CH 2 - ... C m F 2m + 1 CH 2 OCH 2 CH 2 CH 2 - ... C m F 2m + 1 (CH 2) l - ... (Wherein, n is an integer of 1 to 5, m is an integer of 3 to 10, l is an integer of 2 to 6, and R is a hydrogen atom or a methyl group.) At least one selected from the substituents. Also, X, Y, Z are each X
It is an integer of ≧ 0, Y ≧ 1, Z ≧ 1. It was found that the fluorine-containing organopolysiloxane copolymer (fluorine-containing silicone-modified novolac resin) obtained by reacting with the fluorine-containing organopolysiloxane represented by (4) has excellent properties.

That is, when the present inventors generally obtain a copolymer with a novolak resin by using an organopolysiloxane, the water absorption rate of this copolymer tends to increase as compared with the case where the organopolysiloxane is not contained. This is because the organopolysiloxane has a large moisture permeability coefficient, and in order to reduce the water absorption amount, it is effective to introduce a low water-absorbing substituent into the organopolysiloxane molecule, particularly to introduce a fluorine atom. And the novolac resin and above (1)
When the fluorine-containing organopolysiloxane copolymer obtained by reacting with the fluorine-containing organopolysiloxane of the formula is compounded in the epoxy resin composition, not only the water absorption becomes low, but also the glass transition point does not become low and the expansion It was found that an epoxy resin composition having a low coefficient can be obtained, and further, the change of the aluminum electrode due to the stress generated during the heat cycle test is small, the crack test by the immersion of the moisture absorbing solder is good, and the moisture absorption is reduced, Has been completed.

Therefore, the present invention provides a method for producing a fluorine-containing silicone-modified novolac resin, which comprises reacting the novolac resin with the fluorine-containing organopolysiloxane of the above formula (1).

Hereinafter, the present invention will be described in more detail.

The method for producing a fluorine-containing silicone-modified novolac resin (hereinafter, abbreviated as a copolymer) according to the present invention is, as described above, the novolac resin and the following formula (1). [However, R ¹ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, and each R ¹ may be the same or different from each other. R ² is at least one selected from a hydrogen atom or a halogen atom, or a monovalent organic group having an amino group, an epoxy group, a hydroxy group or an alkoxy group, and Rf is represented by the following formula: _{C m F 2m + 1 CH 2} CH 2 OCH 2 CH 2 CH 2 - ... C m F 2m + 1 CH 2 OCH 2 CH 2 CH 2 - ... C m F 2m + 1 (CH 2) l - ... (Wherein, n is an integer of 1 to 5, m is an integer of 3 to 10, l is an integer of 2 to 6, and R is a hydrogen atom or a methyl group.) At least one selected from the substituents. Also, X, Y, Z are each X
It is an integer of ≧ 0, Y ≧ 1, Z ≧ 1. The same applies hereinafter. ] The fluorine-containing organopolysiloxane represented by

Here, as the novolac resin, known phenol novolac resins, epoxy novolac resins, and further alkenyl group-containing novolac resins represented by the following formulas (2) to (9) can be used.

(However, in the above formulas (2) to (9), p and q are usually 1 ≦ p ≦ 2
It is an integer of 0,1 ≦ q ≦ 10. The alkenyl group-containing novolak resins represented by the formulas (2) to (9) are obtained by a usual synthetic method, for example, a phenol resin is reacted with allyl glycidyl ether to introduce an alkenyl group into the molecule, The known epoxy resin can be easily obtained by partially reacting 2-allylphenol or the like.

On the other hand, as the fluorine-containing organopolysiloxane of the above formula (1) used in the present invention, specifically, the following formula (1a)
To (1k) compounds and the like.

Here, the molecular weight of the fluorine-containing organopolysiloxane of the above formula (1) is not necessarily limited, but it is 2000-1000.
0 is preferable. This is because the fluorine-containing organopolysiloxane is incompatible with the epoxy resin matrix, and the molecular weight of the fluorine-containing organopolysiloxane is preferably 2000 to 10,000 in order to form a fine sea-island structure. . If it is 2000 or less, flexibility may not be imparted or a high glass transition temperature may not be obtained when the obtained copolymer is blended with an epoxy resin composition.

Further, in the organopolysiloxane of the formula (1), the amount of the fluorine-containing substituent in the molecule is preferably 3 mol% or more of all the organic groups bonded to silicon atoms, and when it is 3 mol% or less,
When the obtained copolymer is blended with the epoxy resin composition, the water absorption may increase. The water absorption rate of this epoxy resin composition is due to the water repellency of the fluorine atom group, and the water absorption rate decreases as the number of fluorine atoms increases, and conversely, the organopolysiloxane bond has a high moisture permeability coefficient. Therefore, the water absorption of the epoxy resin composition tends to increase as the number of siloxane bonds increases.

Synthesis of the organopolysiloxane of the above formula (1) can be performed, for example, by the following formula. The disiloxane diol represented by Represented by the following formula synthesized by reacting with dichlorosilane in the presence of a tertiary amine such as triethylamine And an organocyclotrisiloxane represented by the following formula, (However, m ′ is an integer of 1 or more. The same shall apply hereinafter.) Organopolysiloxane terminated with a functional end group, and further, if necessary, the following formula: Or the following formula It can be produced by mixing the organocyclotrisiloxane represented by the formula (4) with an appropriate ratio according to the purpose, and polymerizing by a known equilibration reaction using an acid or a base.

In the present invention, the target copolymer can be obtained by subjecting the novolak resin and the fluorine-containing organopolysiloxane of the formula (1) to an addition reaction by a usual method. Specifically, the addition reaction of the alkenyl group-containing novolac resin and the fluorine-containing organopolysiloxane uses a conventionally known addition catalyst, for example, a platinum-based catalyst such as chloroplatinic acid, and a catalyst such as benzene, toluene, or methyl isobutyl ketone. It is preferable to use an active solvent, and the reaction temperature is not particularly limited, but it is preferably 60 to 120 ° C., and the reaction time is usually 30 minutes to 24 hours. Further, a copolymer of an epoxy novolac resin and a fluorine-containing aminopolysiloxane or a copolymer of a phenol novolac resin and a fluorine-containing epoxypolysiloxane can be obtained by reacting each component at room temperature or high temperature. However, it is preferable to use a solvent such as methylisobutylketone, toluene, dioxane, or methylcellosolve in order to mix them in a uniform or nearly uniform state, and to further promote the reaction, water, butanol, isopropyl alcohol, Use alcohols such as ethanol or phenols, amines such as tributylamine and 1,8-diazabicycloundecene-7 as reaction catalysts, organic phosphines such as triphenylphosphine, and 2-phenylimidazole. Use imidazoles Is desirable.

Incidentally, in the present invention, the above-mentioned copolymer, when blended in an epoxy resin composition, does not become compatible with the epoxy resin matrix and has a fine sea-island structure, which is the crack resistance and the adhesion to the element. Is desirable for excellent epoxy resin compositions, and is
The fluorine-containing organopolysiloxane of the formula is such that when the functional group equivalent in the formula (1) is (X) and the molecular weight of the novolac resin is (Y), 1 <(X) / (Y) <25. It is desirable to react at a certain ratio.

The above-mentioned copolymer (fluorine-containing silicone-modified novolac resin) according to the present invention is suitably used as an additive for an epoxy resin composition.

In this case, as the epoxy resin composition, a usual epoxy resin composition containing an epoxy resin and a curing agent is used.

More specifically, the epoxy resin constituting the epoxy resin composition is an epoxy resin having two or more epoxy groups in one molecule, and this epoxy resin can be cured by various curing agents as described below. There are no particular restrictions on the molecular structure, molecular weight, etc., and various conventionally known compounds can be used.

Here, as the epoxy resin, for example, an epoxy resin synthesized from epichlorohydrin and various novolac resins such as bisphenol, an alicyclic epoxy resin or an epoxy resin into which a halogen atom such as chlorine or bromine atom is introduced, and an epoxidized triad. Phenol methane etc. can be mentioned. Of these, novolak type epoxy resins are preferable. The above-mentioned epoxy resin is not necessarily limited to only one kind in use, and two or more kinds may be mixed.

When using the epoxy resin, a monoepoxy compound may be appropriately used in combination. Specific examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, and phenyl glycidyl. Examples include ether, allyl glycidyl ether, octylene oxide, dodecene oxide and the like.

As the curing agent, amine curing agents represented by diaminodiphenylmethane, diaminodiphenyl sulfone, metaphenylenediamine, etc., acid anhydride curing agents such as phthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, etc., Alternatively, a phenol novolac curing agent having two or more hydroxyl groups in one molecule such as phenol novolac and cresol novolac is exemplified.

Further, in the present invention, various curing accelerators such as imidazole or a derivative thereof, a tertiary amine derivative for the purpose of accelerating the reaction between the curing agent and the epoxy resin described above,
There is no problem with using a phosphine derivative, a cycloamidine derivative or the like together.

The amount of the curing agent used is the amount usually used,
The compounding amount of the curing accelerator can be set within the usual range.

Further, the epoxy resin composition of the present invention may contain an inorganic filler. In this case, the inorganic filler is blended in a usual amount, and there is no limitation on the type of the inorganic filler, a single use or a combination of a plurality of types, and it is appropriately selected according to the application of the epoxy resin composition, for example, Crystalline silica,
One or more selected from natural silica such as amorphous silica, synthetic high-purity silica, synthetic spherical silica, talc, mica, silicon nitride, boron nitride, alumina and the like can be used.

The composition of the present invention may further contain various additives, if necessary, depending on the purpose, application and the like. For example, waxes, fatty acids such as stearic acid and release agents such as metal salts thereof, pigments such as carbon black, dyes, antioxidants, flame retardants, surface treatment agents (γ-glycosideoxypropyl tolumethoxysilane, etc.) However, there is no problem in blending other additives.

The above-mentioned copolymer (fluorine-containing silicone-modified novolac resin) can be blended in such an epoxy resin composition. In this case, the blending amount of the copolymer in the epoxy resin composition is that of the epoxy resin and the curing amount. The total amount of the agent is preferably 1 to 100 parts by weight, particularly preferably 2 to 60 parts by weight, and when the compounding amount is less than 1 part by weight, the glass transition point of the epoxy resin composition is improved and the resistance is improved. In some cases, the effect of improving the cracking property and suppressing the movement of aluminum wiring may be insufficient, and when it exceeds 100 parts by weight, the mechanical strength of the epoxy resin composition tends to decrease.

This epoxy resin composition is prepared by uniformly stirring and mixing the predetermined amounts of the above-mentioned components, and kneading with a kneader, roll, extruder or the like which has been heated to 70 to 95 ° C., cooling, and pulverizing. Obtainable. There is no particular limitation on the order of mixing the components.

The epoxy resin composition of the present invention can be suitably used as a molding material and a powder coating material, and also for sealing semiconductor devices such as ICs, LSIs, transistors, thyristors, and diodes.
It can be effectively used for manufacturing printed circuit boards.

The semiconductor device can be sealed by a conventionally used molding method such as transfer molding, injection molding, or casting method. In this case, the molding temperature of the epoxy resin device is 150-180
It is preferable that the post-curing is performed at 150 to 180 ° C. for 2 to 16 hours.

As described above, according to the production method of the present invention, it is possible to easily produce a fluorine-containing silicone-modified novolac resin that is preferably used as an epoxy resin composition additive, and this fluorine-containing silicone-modified Epoxy resin composition containing novolac resin does not decrease mechanical strength such as bending strength and bending elasticity, has a low expansion coefficient, high glass transition point and excellent crack resistance, and has a small amount of aluminum electrode deformation. It is also possible to obtain an epoxy resin composition which has low water absorption and can be suitably used as a molding material, a powder coating material, a semiconductor sealing material, or the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following examples, all parts are parts by weight.

[Examples 1 to 12] The cresol novolac resin and allyl glycidyl ether were placed in a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, and the mixture was reacted, and then epichlorohydrin was further added to react. Epoxidized by the usual method of allowing alkenyl group-containing cresol novolac epoxy resin (alkenyl equivalent 1500,
Epoxy equivalent 270, hydrolyzable chlorine 700ppm) was obtained.

In a four-necked flask similar to the above, 120 g of alkenyl group-containing cresol novolac epoxy resin obtained by the above method, 100 g of methyl isobutyl ketone, 200 g of toluene, 0.04 g of 2-ethylhexanol-modified chloroplatinic acid solution of 2% platinum concentration, respectively. After 1 hour of azeotropic dehydration, 50 g of the fluorine-containing organopolysiloxane shown in Table 1 was added dropwise at the reflux temperature for 30 minutes, and the mixture was stirred at the same temperature for 4 hours and reacted, The obtained contents were washed with water and the solvent was distilled off under reduced pressure to obtain reaction products (copolymers A to L) shown in Table 1.

[Example 13] A cresol novolac resin and allyl glycidyl ether were placed in a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, and the mixture was reacted, and then an alkenyl group-containing cresol novolac epoxy resin ( Alkenyl equivalent of 1500 and phenol equivalent of 110) were obtained.

In a four-neck flask similar to the above, 120 g of alkenyl group-containing cresol novolac resin obtained by the above method, 100 g of methyl isobutyl ketone, 200 g of toluene, and 0.04 g of 2-ethylhexanol-modified chloroplatinic acid solution having a platinum concentration of 2% were placed. After azeotropic dehydration for 1 hour, 50g of fluorine-containing organopolysiloxane shown in Table 1 was added at the reflux temperature for 3 hours.
The mixture was added dropwise at 0 minutes, and the mixture was stirred at the same temperature for 4 hours for reaction, and the obtained contents were washed with water, and the solvent was distilled off under reduced pressure to give the reaction products shown in Table 1 ( A copolymer M) was obtained.

Example 14 A four-necked flask having an internal volume of 1 equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel had a softening point of 70.
℃ epoxidized cresol novolac resin (epoxy equivalent 200) 120g, 1,4-dioxane 150g, n-butanol 150g
Add the following compound while stirring at a temperature of 83 ° C. 50 g was added dropwise at a dropping time of 2 hours, and the reaction was continued by stirring at the same temperature for 6 hours. Then, the solvent was distilled off from the obtained contents to obtain reaction products (copolymer N) shown in Table 1.

[Example 15] 32 g of allylphenol, 200 g of toluene, 200 g of methyl isobutyl ketone, 2% in a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel.
2-ethylhexanol modified chloroplatinic acid solution with platinum concentration
Add 0.04 g of each and carry out azeotropic dehydration for 1 hour. At the reflux temperature, 40 g of fluorine-containing organopolysiloxane was added dropwise at a dropping time of 30 minutes, and after stirring at the same temperature for 4 hours to react, The obtained contents are washed with water, unreacted allylphenol, by distilling off the solvent under reduced pressure,
The following compound was obtained.

In a four-necked flask similar to the above, 50 g of the fluorogenic organopolysiloxane containing phenolic OH and the orthocresol novolac epoxy resin (epoxy equivalent 20
0, hydrolyzable chlorine (700 ppm) (120 g) and toluene (400 g) were added, dissolved at the reflux temperature, and then stirred at the same temperature for 2 hours. After that, the solvent is distilled off under reduced pressure to
The reaction product (copolymer O) shown in the table was obtained.

Example 16 In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 40 g of allyl glycidyl ether, 400 g of toluene, and 0.04% 2-ethylhexanol-modified chloroplatinic acid solution having a platinum concentration of 2% were added. Add each g and azeotropic dehydration for 1 hour, then add 40g of fluorine-containing organopolysiloxane with SiH functional group at the reflux temperature for 3 hours.
After dropping at 0 minutes and further stirring at the same temperature for 4 hours to react, the obtained content is washed with water, and unreacted allyl glycidyl ether and the solvent are distilled off under reduced pressure.
The following compound was obtained.

Into a four-necked flask similar to the above, 50 g of the epoxy group-containing fluorine-containing organopolysiloxane obtained by the above method, 120 g of orthocresol novolac resin (OH equivalent 110), and 400 g of methyl isobutyl ketone were placed and dissolved at reflux temperature, and then 2 Stir at the same temperature for hours. Then, the solvent was distilled off under reduced pressure to obtain a reaction product (copolymer P) shown in Table 1.

[Example 17] 120 g of orthocresol novolac resin (OH equivalent 110) and 400 g of methyl isobutyl ketone were placed in a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, and dissolved at a reflux temperature. , Then 2 hours
Water is removed by adding 16 g of 50% NaOH aqueous solution and performing azeotropic dehydration. Then at reflux temperature 50 g of the following compound Was dropped in 30 minutes. Further, stirring was continued at the same temperature for 2 hours to cause a reaction. Then, it was washed with water and the solvent was distilled off to obtain a reaction product (copolymer Q) shown in Table 1.

[Comparative Examples 1 to 4] In the same manner as in Example 1, an alkenyl group-containing cresol novolac epoxy resin was reacted with a fluorine-containing organopolysiloxane shown in Table 1 to give a reaction product (copolymerization) shown in Table 1. Combined R, X-Z) was obtained.

* Fluorine-containing substituent Rf V CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − VI CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − VII CF ₃ (CF ₂ ) ₇ CH ₂ CH _{2 OCH 2 CH 2 CH 2 - VIII} CF 3 (CF 2) 3 CH 2 CH 2 - IX CF 3 CH 2 CH 2 - Next, by using the copolymer obtained in the above examples and Comparative examples, the following Thus, an epoxy resin composition was obtained.

Epoxidized cresol novolac resin (curable epoxy resin) having an epoxy equivalent of 200 and phenol novolac resin having a phenol equivalent of 110 were used in the respective compounding amounts shown in Table 2, and the copolymers obtained in the above Examples and Comparative Examples were used. Of these, 16 parts of those shown in Table 2 were mixed, and 10 parts of brominated epoxy novolac resin, 260 parts of quartz powder, γ-
21 parts of epoxy resin composition were prepared by adding 1.5 parts of glycidoxypropyltrimethoxysilane, 1.5 parts of wax E and 1.0 part of carbon black, and uniformly mixing the resulting mixture with a hot two-roll mill to obtain 21 kinds of epoxy resin compositions. No. 1 to 17 and Comparative Examples No. 1 to 4) were manufactured.

For these epoxy resin compositions, the following (a) ~
Various tests (g) were conducted.

(A) Spiral flow value It was measured under the conditions of 175 ° C and 70 kg / cm ² using a mold conforming to the EMMI standard.

(B) Mechanical strength (bending strength and bending elastic modulus) A 10 × 4 × 100 mm bending bar was molded according to JIS K6911 under conditions of 175 ° C., 70 kg / cm ² and molding time of 2 minutes. It measured about what was post-cured for time.

(C) Using a test piece having a coefficient of expansion and a glass transition temperature of 4 mmφ × 15 mm, the value when the temperature was raised at a rate of 5 ° C. per minute was measured by a dilatometer.

(D) Crack resistance 9.0 x 4.5 x 0.5 mm silicon chip with 14 PIN-IC
After adhering to a frame (42 alloy) and molding the epoxy resin composition on this under molding conditions of 175 ° C x 2 minutes and post-curing at 180 ° C for 4 hours, -196 ° C x 1 minute to 260 ° C x 30 seconds Heat cycle was repeated and the resin crack occurrence rate after 200 cycles was measured (test number = 50). (E) Deformation amount of aluminum electrode Aluminum electrode was vapor-deposited on a silicon chip with a size of 3.4 x 10.2 x 0.3 mm. The deformation amount measuring element was bonded to a 14-pin IC frame (42 alloy), and the epoxy resin composition was molded on this at 180 ° C for 2 minutes and post-cured at 180 ° C for 4 hours, then at -196 ° C x A thermal cycle of 1 minute to 260 ° C. × 30 seconds was repeatedly applied, and the amount of deformation of the aluminum electrode after 200 cycles was examined (the number of tests = 3).

(F) Moisture resistance A sample molded into a 14-pin DIP IC shape was placed in a high-pressure oven at 121 ° C and 100% humidity for 100 hours, and the open defect rate of the wiring was examined.

(G) Using a test piece with water absorption of 50 mmφ and thickness of 3 mm, 85 ℃ / 85% RH, 100h
r Measured by the rate of weight increase after standing.

The results of the above tests are also shown in Table 2.

From the results shown in Table 2, the epoxy resin composition containing the copolymer obtained by the reaction of the novolac resin according to the present invention and the fluorine-containing organopolysiloxane was found to be an epoxy resin composition containing no copolymer. Mechanical strength such as flexural strength and flexural modulus is not impaired, and the coefficient of expansion is equal to or less than that of materials, and also has a high glass transition temperature and excellent crack resistance, and the amount of deformation of the aluminum electrode is small. It was found that the moisture resistance was good and the water absorption rate was small.

Continuation of front page (72) Inventor Toshio Shiobara 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Reference JP-A-58-21417 (JP, A) JP-A-63-142024 (JP, A)

Claims (1)

[Claims] 1. A novolac resin and the following formula (1): (However, in the formula, R ¹ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, and each R ¹ may be the same as or different from each other.
R ² is a hydrogen atom, amino group, epoxy group, hydroxy group,
Halogen atom or alkoxy group, Rf is the following formula _{C m F 2m + 1 CH 2} CH 2 OCH 2 CH 2 CH 2 - ... C m F 2m + 1 CH 2 OCH 2 CH 2 CH 2 - ... C m F 2m + 1 (CH 2) l - ... (Wherein, n is an integer of 1 to 5, m is an integer of 3 to 10, l is an integer of 2 to 6, and R is a hydrogen atom or a methyl group.) At least one selected from the substituents. Also, X, Y, Z are each X
It is an integer of ≧ 0, Y ≧ 1, Z ≧ 1. And a fluorine-containing organopolysiloxane represented by the formula (4) is reacted.