JPH0686583B2 - Film-forming agent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition in which a curing reaction is promoted by a radical reaction initiator to form a cured film.

[0002]

2. Description of the Related Art A release agent composition containing an organosilazane polymer as a main component (JP-A-60-145815 and JP-A-60-2214).
70) is known to form a water-repellent cured film.

[0003]

However, in order to sufficiently cure the above releasing agent composition, a long time treatment is required. Further, the water repellency of the obtained cured film is not at a satisfactory level. Therefore, an object of the present invention is to provide a composition which can be cured in a short curing time and can form a film having good water repellency.

[0004]

The present invention comprises (a) the following [A]:
The unit represented by the general unit formula [I] of the group, and optionally the unit represented by the general unit formula [II] and the general unit formula [III], and the general unit formula [IV] of the group [B] below. And a unit represented by the general unit formula [V] and a unit represented by the general unit formula [VI], and,
The ratio of the constitutional unit of group [A] to the constitutional unit of group [B] is R ⁴
/ (R ¹ + R ² ) [wherein R ¹ and R ² are as defined by the following general unit formula [I], and R ⁴ is as defined by the following general unit formula [IV] . ] Molar ratio
An organosilazane copolymer in the range of 99/1 to 50/50; [A] group: general unit formula [I]: [R ¹ (CH ₂ ) _m ] _aR ² _b Si (NR ³ ) _{(4 -ab) / 2} [I] (in the above formula, R ¹ represents an unsaturated fatty acid ester group,
R ² and R ³ may be the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group, a represents an integer of 1 to 3, b represents an integer of 0 to 2, and a + b represents 1 to 3. Is an integer and m represents an integer of 2 to 5. ) General unit formula [II]: [R ¹ (CH ₂ ) _m ] _a R ² _b SiO _{(4-ab) / 2} [II] (In the above formula, R ¹ , R ² , a, b and m are as described above. General unit formula [III]: [R ¹ (CH ₂ ) _m ] _c R ² _d SiO _{e / 2} (NR ³ ) _{f / 2} [III] (in the above formula, R ¹ , R ² , R ³ and m are as described above, c represents an integer of 0 or 1, and d, e and f
Represents an integer of 1 or 2, and c + d + e + f is 4. ) [B] group: general unit formula [IV]: [R ⁴ (CH ₂ ) _n ] _m R ² _h Si (NR ³ ) _{(4-gh) / 2} [IV] (wherein R ⁴ is a per Represents a fluoroalkyl group, R
² and R ³ are as described above, g represents an integer of 1 to 3, h represents an integer of 0 to 2, g + h is an integer of 1 to 3, and n represents an integer of 2 to 5. . ) General unit formula ^{[V]: [R 4 (} CH 2) n] g R 2 h SiO (4-gh) / 2 [V] ( in the ^{formula, R 2, R 4, g} , h and n are the General unit formula [VI]: [R ⁴ (CH ₂ ) _n ] _i R ² _j SiO _{k / 2} (NR ³ ) _{l / 2} [VI] (in the above formula, R ² , R ³ , R ⁴ and n are as described above, i represents an integer of 0 or 1, and j, k and l
Represents an integer of 1 or 2, and i + j + k + l is 4. The present invention provides a film forming composition comprising (b) an oil-soluble radical reaction initiator and (c) an organic solvent.

The organosilazane copolymer of (a) is a unit represented by the general unit formula [I] of the [A] group and a general unit of the [B] group. The unit represented by the formula [IV] is an essential constituent unit.

In the general unit formula representing the constitutional unit of the [A] group, R
¹ must be an unsaturated fatty acid ester group. Examples of the unsaturated fatty acid ester group include an acryloxy group and a methacryloxy group, and among them, a methacryloxy group is preferable. R ² and R ³ may be the same or different and each is a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group preferably has 1 to 8 carbon atoms. Specifically, a methyl group, an ethyl group, an alkyl group such as a propyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group, an aryl group such as a tolyl group,
Examples thereof include cycloalkyl groups such as cyclohexyl group. R ² is preferably a methyl group, and R ³ is preferably a hydrogen atom.

A is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is an integer of 1 to 3. c is an integer of 0 or 1, d, e and f are integers of 1 or 2, and c + d + e + f is 4. m is an integer of 2 to 5, preferably 3.

In the general unit formula representing the constitutional unit of the [B] group, R
⁴ must be a perfluoroalkyl group, and preferably has 4 to 20 carbon atoms. As such a perfluoroalkyl group eg -C ₄ F _9, -C ₆ F
_{13, -C 8 F 17, -C} 10 F 21, -C 12 F 25, -C 14 F 29
And the like, more preferably -C ₈ F _17.

G is an integer of 1 to 3, h is an integer of 0 to 2, and g + h is an integer of 1 to 3. i is an integer of 0 or 1, j, k and l are integers of 1 or 2, and i + j + k + l is 4. n is an integer of 2 to 5, preferably 2.

In the organosilazane copolymer of the component (a),
The ratio of the constitutional unit of the [A] group to the constitutional unit of the [B] group is as follows: unsaturated fatty acid ester group: R ¹ , hydrogen atom or 1
Valent hydrocarbon groups: R ² and perfluoroalkyl groups:
The molar ratio of ^{R 4: R 4 / (R} 1 + R 2) is required to be in the range of 99 / 1-50 / 50. More preferably 95/5 to 60
It is in the range of / 40. If the molar ratio is out of the above range, the resulting film will not have good water repellency.

Specific examples of the organosilazane copolymer as the component (a) described above include those represented by the following formula.

[Chemical 1]

[Chemical 2]

[Wherein k, l, m, and n are arbitrary integers as long as R ⁴ / (R ¹ + R ² ) is in the range of 99/1 to 50/50. ]

The organosilazane copolymer in the present invention is
It may contain units other than the constituent units of the above-mentioned [A] group and constituent units of the [B] group. As such a unit, for example,
General unit formula [VII]: R ² _p Si (NR ³ ) _{(4-p) / 2} [VII] (wherein R ² and R ³ are as described above, p
Is an integer of 1 to 3. Unit represented by the general formula [VIII]: R ² _p SiO _{(4-p) / 2} [VIII] (wherein R ² and p are as described above). General unit formula [IX]: R ² _v SiO _{w / 2} (N R ³ ) _{x / 2} [IX] (wherein R ² and R ³ are as described above, and v and w
And x represent an integer of 1 or 2, and v + w + x is 4. ) And the like.

By introducing the units represented by the above formulas [VIII] to [IX], the water repellency and hardness of the organosilazane copolymer can be improved.
Note that in the above case also, the molar ratio of said organo silazane ^{copolymer: R 4 / (R 1 +} R 2) is 99
It is preferably in the range of / 1 to 50/50. More preferably, it is in the range of 95/5 to 60/40.

The method for obtaining the organosilazane copolymer as the component (a) is described in USP 2564674, JP-A-60-141758, and JP-A-60-158758.
-145815, JP-A-60-221470 and the like. For example, according to JP-A-60-221470, in order to introduce an essential structural unit of the [A] group, the following general formula [X]: [R ¹ (CH ₂ ) _m ] _a R ² _b SiX _4-ab [X] (In the above formula, x represents a halogen atom, R ¹ , R ² ,
m, a and b are as described above. Organohalosilane represented by), and optionally, the general composition formula shown further below ^{[XI]: [R 1 (} CH 2) m] A R 2 B X C SiO (4-ABC) / 2 [XI (In the above formula, R ¹ , R ² , X and m are as described above, A is 0.001 <A <2.5, and B is 0 ≦ <B <2.
5 and C is 0.001 <C <2. ), And a general formula [XII]: [R ⁴ (CH ₂ ) _m ] _g R ² _h shown below for introducing the essential structural unit of the [B] group. An organohalosilane represented by SiX _4-gh [XII] (in the above formula, R ² , R ⁴ , n, g, h and X are as described above), and optionally, further shown below. General compositional formula [XIII]: [R ⁴ (CH ₂ ) _m ] _D R ² _E X _F SiO _{(4-DEF) / 2} [XIII] (wherein R ² , R ⁴ , n and X are as defined above). And D is 0.001 <D <2.5 and E is 0 ≦ <E <2.
5 and F is 0.001 <F <2. ), And a method of reacting a mixture of the organohalosiloxane represented by the formula (4) with ammonia or a primary amine in an organic solvent.

Further, the general unit formula [VII] shown above,
In order to introduce the units represented by the general unit formulas [VIII] and [IX] into the organosilazane copolymer, the following units corresponding to the units represented by the general unit formula [VII] shown above may be used, if necessary. An organohalosilane represented by the general formula [XIV]: R ² _p SiX _4-p [XIV] (wherein R ² , X and p are as described above), and / or the above The general composition formula [XV]: [R ¹ (CH ₂ ) containing the units represented by the general unit formulas [VIII] and [IX] shown in
_m ] _G [R ⁴ (CH ₂ ) _n ] _H R ² _I X _J SiO
_{(4-GHIJ) / 2} [XV] (in the above formula, R ¹ , R ² , R ⁴ ,
m, n and X are as described above, and G is 0 ≦ G <2.
5, H is 0 ≦ H <2.5, and I is 0 <I <2.5
And J is 0 <J <2. The organohalosiloxane represented by the formula (1) may be subjected to the reaction together with the above mixture or in place of the above organohalosiloxane. Examples of the organohalosilane represented by the above general formula [XIV] include CH ₃ SiCl ₃ and (CH ₃ ) ₂ SiCl.
₂ , (C ₆ H ₅ ) SiCl ₃ , and (CH ₃ ) (C ₆ H ₅ ) SiCl ₂ . In addition, the general composition formula [XV] shown above
Examples of the organohalosiloxane represented by

[Chemical 3] (In the above formula, m and n are R ⁴ / (R ¹ + R ² ).
Is an arbitrary integer as long as it is in the range of 99/1 to 50/50. ) And the like.

The radical reaction initiator of (b) The radical reaction initiator of (b) needs to be soluble in an organic solvent. Examples of such an oil-soluble radical reaction initiator include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile (AIBN), cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, hyponitrite. , Phenylazotriphenylmethane, diazothioether, diazoaminobenzene, azodibenzoyl and the like. Among them, azobisisobutyronitrile is particularly preferable.

The amount of component (b) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of component (a). If the amount of component (b) is too small, the film forming agent composition will not be sufficiently cured. Also,
If the amount is too large, the component (b) tends to precipitate in the composition, and the resulting cured film has insufficient water repellency.

The organic solvent of (c) The organic solvent of (c) preferably has excellent dissolving power for the above-mentioned components (a) and (b). Examples of such an organic solvent include fluorohydrocarbons, and specifically, for example, trichlorotrifluoroethane, tetrachlorodifluoroethane, dichloromonofluoroethane,
Dichlorotrifluoroethane, bromochlorotrifluoroethane, metaxylene hexafluoride and the like can be mentioned. Further, to these fluorohydrocarbons, for example, dichloroethane, trichloroethane, chlorinated hydrocarbons such as methylene chloride, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, dipropyl ether, ethers such as dibutyl ether, n- Pentane,
Saturated hydrocarbons such as n-hexane, n-heptane, cyclohexane and petroleum ether may be added as necessary.

The amount of the above organic solvent is preferably such that the concentrations of the component (a) and the component (b) in the solvent are each 0.1 to 30% by weight. The amount is more preferably 1 to 5% by weight. If the amount of the organic solvent is too small, the cured film will have insufficient water repellency. On the other hand, when the amount is too large, it takes a long time to volatilize the organic solvent and a long time is required for curing.

The organic solvent as the component (c) can be used as a reaction solvent when synthesizing the organosilazane polymer as the component (a). In such a case, it is possible to obtain the organosilazane polymer as the component (a) as a homogeneous solution, and then add the radical reaction initiator as the component (b) to obtain the composition of the present invention. be able to.

Curing Method The composition of the present invention can be cured by heat. The curing temperature may be about 100 ° C. Further, since the curing reaction is promoted by the radical reaction initiator (b), the curing time of this composition is as short as about 10 minutes.

Uses The cured film formed from the film forming composition of the present invention has good water repellency. Therefore, the film forming agent composition of the present invention can be used as a water repellent agent for window glass of automobiles, ships, railway vehicles and the like.

[0024]

Example 1 Methacryloxy group-containing trichlorosilane of the following formula

[Chemical 4] 3.0 g (1.1 × 10 ^-2 mol) and 58.2 g (1.0 × 10 ^-1 mol) of fluorine-containing trichlorosilane C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ represented by the following formula were dissolved in 200 ml of trichlorotrifluoroethane. After cooling this solution to 5 ° C, ammonia gas was blown into the solution for 2 hours while maintaining the liquid temperature at 20 ° C or lower. After that, heating under reflux was performed for 30 minutes to remove excess ammonia dissolved in the solution. After cooling the solution to 5 ° C again,
By-product ammonium chloride was filtered off from the solution,
A colorless and transparent solution containing the organosilazane copolymer was obtained.

The solution obtained above was then diluted to 1% by weight with trichlorotrifluoroethane. Further, 1 part by weight of 2,2′-azobisisobutyronitrile as a radical reaction initiator was added to 100 parts by weight of the diluted solution of the organosilazane copolymer to obtain the desired film forming composition. . In this case, in the case of R ⁴ / (R ¹
+ Molar ratio of -C ₈ F ₁₇ group / methacryloxy group corresponding to R ²⁾ was 90/10.

Further, the obtained film forming agent composition is coated on a glass substrate so as to have a thickness of about 0.5 μm and cured at a temperature of 105 ° C. for 10 minutes, and then the uncured portion on the surface is wiped off. Was wiped off to form a film.

Example 2 The amount of methacryloxy group-containing trichlorosilane used in Example 1 was changed to 5.8 g (2.2 × 10 ^-2 mol) and the amount of fluorine-containing trichlorosilane was changed to 46.5 g (8.0 × 10 ^-2 mol). A film forming agent composition was obtained in the same manner as in Example 1 except that
In this case, the molar ratio of —C ₈ F ₁₇ group / methacryloxy group corresponding to R ⁴ / (R ¹ + R ² ) is:
It was 80/20.

Further, a cured film was formed from the obtained film forming agent composition in the same manner as in Example 1.

Example 3 The amount of methacryloxy group-containing trichlorosilane used in Example 1 was changed to 11.5 g (4.4 × 10 ^-2 mol), and the amount of fluorine-containing trichlorosilane was 34.9 g (6.0 × 10 ^-2 mol). A film forming agent composition was obtained in the same manner as in Example 1 except that
In this case, the molar ratio of —C ₈ F ₁₇ group / methacryloxy group corresponding to R ⁴ / (R ¹ + R ² ) is:
It was 60/40.

Further, a cured film was formed from the obtained film forming agent composition in the same manner as in Example 1.

Example 4 The amount of methacryloxy group-containing trichlorosilane used in Example 1 was changed to 3.0 g (1.1 × 10 ^-2 mol), and the amount of fluorine-containing trichlorosilane was changed to 57.4 g (9.9 × 10 ^-2 mol). 0.2g (1.1 × 10 ^-3 mol) of trichloromethylsilane
A film forming composition was obtained in the same manner as in Example 1 except that was added. In this case, in the case of R ⁴ / (R
¹ + R ²⁾ corresponding to -C ₈ F ₁₇ group / (molar ratio of methacryloxy group + methyl group) was 90/10. further,
A cured film was formed from the obtained film forming agent composition in the same manner as in Example 1.

Comparative Example 1 A colorless and transparent solution containing an organosilazane copolymer obtained in the same manner as in Example 1 was used except that 2,2'-azobisisobutyronitrile as the component (b) was not added. A film forming agent composition was obtained in the same manner as in Example 1. This composition was applied to a glass substrate in the same manner as in Example 1 and cured by heating at 105 ° C. for 2 hours. Then, the composition of the uncured component on the surface of the obtained cured product was removed using a wiping paper to obtain a cured film.

Comparative Example 2 Instead of the methacryloxy group-containing trichlorosilane used in Comparative Example 1, 1.5 g (1.2 × 10 ⁻² mol) of dichlorodimethylsilane and the fluorine-containing trichlorosilane used in Comparative Example 1 were replaced by A cured film was obtained in the same manner as in Comparative Example 1 except that 58.2 g (10.0 × 10 ^-2 mol) of fluorine-containing trichlorosilane C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ represented by the following chemical formula was used.

Comparative Example 3 Without using methacryloxy group-containing trichlorosilane,
A cured film was prepared in the same manner as in Comparative Example 1 except that fluorine-containing trichlorosilane represented by the following chemical formula C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ 60.0 g (10.3 × 10 ^-2 mol) was used as the fluorine-containing trichlorosilane. Obtained.

In order to investigate the water repellency of the cured coatings obtained in the above Examples 1 to 4 and Comparative Examples 1 to 3, the water drop angle was measured. In this measurement, using a static friction coefficient measuring device (manufactured by Shinto Scientific Co., Ltd.), at a temperature of 25 ° C., 16 mm / sec.
The sample plate was raised at the speed of, and the angle at which the water droplets started falling was measured. It can be said that the smaller the water drop angle is, the better the water repellency of the film is. The results of the above measurements are shown in Table 1.

[0036]

From Table 1 above, it can be seen that in the water drop sliding angle for the obtained cured film, the measurement result of the example shows a smaller value than the measurement result of the comparative example.
From this, it is understood that the cured film obtained by curing the composition obtained in the example has excellent water repellency.

[0038]

The film forming agent composition of the present invention can be cured in a short curing time and can form a film having good water repellency.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masanori Sudo, Masanori Sudo, 13-1, Isobe, Gunma Prefecture 2-13-1 Isobe Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (2)

[Claims] (A) A unit represented by the general unit formula [I] of the following [A] group, and optionally a unit represented by the general unit formula [II] and the general unit formula [III]: A unit represented by the general unit formula [IV] of the following [B] group, and optionally a unit represented by the general unit formula [V] and the general unit formula [VI], and [ The ratio of the constitutional unit of the A group to the constitutional unit of the [B] group is R ⁴ / (R ¹ + R ² ) [wherein R ¹ and R ² are as defined by the following general unit formula [I]. And R ⁴ is as defined in the following general unit formula [IV]. Organosilazane copolymer having a molar ratio of] of 99/1 to 50/50; [A] group: general unit formula [I]: [R ¹ (CH ₂ ) _m ] _a R ² _b Si ( NR ³ ) _{(4-ab) / 2} [I] (wherein R ¹ represents an unsaturated fatty acid ester group,
R ² and R ³ may be the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group, a represents an integer of 1 to 3, b represents an integer of 0 to 2, and a + b represents 1 to 3. Is an integer and m represents an integer of 2 to 5. ) General unit formula [II]: [R ¹ (CH ₂ ) _m ] _a R ² _b SiO _{(4-ab) / 2} [II] (In the above formula, R ¹ , R ² , a, b and m are as described above. General unit formula [III]: [R ¹ (CH ₂ ) _m ] _c R ² _d SiO _{e / 2} (NR ³ ) _{f / 2} [III] (in the above formula, R ¹ , R ² , R ³ and m are as described above, c represents an integer of 0 or 1, and d, e and f
Represents an integer of 1 or 2, and c + d + e + f is 4. ) [B] group: general unit formula [IV]: [R ⁴ (CH ₂ ) _n ] _m R ² _h Si (NR ³ ) _{(4-gh) / 2} [IV] (wherein R ⁴ is a per Represents a fluoroalkyl group, R
² and R ³ are as described above, g represents an integer of 1 to 3, h represents an integer of 0 to 2, g + h is an integer of 1 to 3, and n represents an integer of 2 to 5. . ) General unit formula ^{[V]: [R 4 (} CH 2) n] g R 2 h SiO (4-gh) / 2 [V] ( in the ^{formula, R 2, R 4, g} , h and n are the General unit formula [VI]: [R ⁴ (CH ₂ ) _n ] _i R ² _j SiO _{k / 2} (NR ³ ) _{l / 2} [VI] (in the above formula, R ² , R ³ , R ⁴ and n are as described above, i represents an integer of 0 or 1, and j, k and l
Represents an integer of 1 or 2, and i + j + k + l is 4. ) A film forming composition comprising (b) an oil-soluble radical reaction initiator and (c) an organic solvent. 2. A cured film obtained by curing the film-forming agent composition according to claim 1.