JPWO2014207886A1 - Coating agent containing silicon oligomer and use thereof - Google Patents

Abstract

（ただし、Ｒ_１〜Ｒ_１０はそれぞれ独立して炭素数１〜４のアルキル基またはヒドロキシ アルキル基であり、Ｘ_１〜Ｘ_３はそれぞれ独立して次の一般式（II）
【化２】

（ただし、Ａは炭素数２〜４の分岐していてもよいアルキレン基であり、ｌは１〜 ３の整数である）
で表される基であり、ｎは０または１であり、ｍはｎが０のときは１〜３の整数で あり、ｎが１のときは１である）
で表されるシリコンオリゴマーを含有することを特徴とするコーティング剤およびこれを用いた表面処理方法を提供する。For the purpose of providing a coating agent using a novel silicon oligomer having a novel function, which is not found in conventional water-tetraalkoxysilane condensates, the following general formula (I)
[Chemical 1]

(However, R < ₁ > -R < ₁₀ > is respectively independently a C1-C4 alkyl group or a hydroxy alkyl group, and X < ₁ > -X < ₃ > is respectively independently the following general formula (II)
[Chemical formula 2]

(However, A is an alkylene group having 2 to 4 carbon atoms which may be branched, and l is an integer of 1 to 3)
Wherein n is 0 or 1, m is an integer of 1 to 3 when n is 0, and 1 when n is 1)
The coating agent characterized by containing the silicon oligomer represented by this, and the surface treatment method using the same.

Description

  The present invention relates to a coating agent containing a novel silicon oligomer, a surface treatment method using the coating agent, and a surface-treated product obtained by treatment with the coating agent.

  A number of methods have been reported so far in which a film is formed using a condensate of water and tetraalkoxysilane and an inorganic-organic hybrid coating is applied to a member to be treated (Non-patent Document 1).

  However, since the condensate has a short interelectrode distance, there is a problem that the film obtained after coating and heat treatment becomes hard, particularly when this film is provided on a fastening member. At the same time, it has been difficult to cope with functionality such as the coefficient of friction.

  Further, the coating liquid containing the condensate has a problem in stability, and the hydrolysis progresses with the passage of time, so that the sol-gel property cannot be maintained.

Kazutoshi Iwamoto et al., “Functionalization of Inorganic / Organic Composite Materials by Sol-Gel Method”, Production Research, Vol. 42, No. 8, pp. 466-473, 1990

  The subject of this invention is providing the coating agent using the novel silicon oligomer which has a novel function which is not in the conventional condensate of water and tetraalkoxysilane which can solve said problem.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have discovered that a novel interfacial distance between silicon atoms is long by reacting a tetraalkoxysilane having a specific structure with a dihydric alcohol having a specific structure. It has been found that a silicon oligomer can be obtained. And when a to-be-processed member was processed with the coating agent using this silicon oligomer, it discovered that corrosion resistance and functionality could be provided, and completed this invention.

（ただし、Ｒ_１〜Ｒ_１０はそれぞれ独立して炭素数１〜４のアルキル基またはヒ ドロキシアルキル基であり、Ｘ_１〜Ｘ_３はそれぞれ独立して次の一般式（II）

（ただし、Ａは炭素数２〜４の分岐していてもよいアルキレン基であり、 ｌは１〜３の整数である）
で表される基であり、ｎは０または１であり、ｍはｎが０のときは１〜３ の整数であり、ｎが１のときは１である）
で表されるシリコンオリゴマー。
（２）上記シリコンオリゴマーを加熱処理して得られる重合性生成物。
（３） 次の一般式（III）

（ただし、Ｒ_１１〜_１４はそれぞれ独立して炭素数１〜４のアルキル基または ヒドロキシアルキル基である）
で表されるテトラアルコキシシランと、次の一般式（IV）

（ただし、Ｂは炭素数２〜４の分岐していてもよいアルキレン基であり、 ｋは１〜３の整数である）
で表される２価アルコールを、金属触媒、酸またはアルカリの存在下で反応させることを特徴とする上記シリコンオリゴマーの製造方法。
（４）上記シリコンオリゴマーを含有するコーティング剤。
（５）被処理部材を、上記コーティング剤で処理することを特徴とする表面処理方法。
（６）被処理部材を、上記コーティング剤で処理することにより得られる表面処理製品。That is, this invention is the following (1)-(6).
(1) General formula (I)

(Wherein R _{1 to} R ₁₀ are each independently an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and X _{1 to} X ₃ are each independently represented by the following general formula (II):

(However, A is an alkylene group having 2 to 4 carbon atoms which may be branched, and l is an integer of 1 to 3)
N is 0 or 1, m is an integer of 1 to 3 when n is 0, and 1 when n is 1)
Silicon oligomer represented by
(2) A polymerizable product obtained by heat-treating the silicon oligomer.
(3) The following general formula (III)

_{(Wherein, R} 11 _{~ 14} is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms each independently)
And a tetraalkoxysilane represented by the following general formula (IV)

(However, B is a C2-C4 alkylene group which may be branched, and k is an integer of 1-3.)
A process for producing a silicon oligomer as described above, wherein the dihydric alcohol represented by the formula is reacted in the presence of a metal catalyst, an acid or an alkali.
(4) A coating agent containing the above silicon oligomer.
(5) A surface treatment method characterized by treating a member to be treated with the coating agent.
(6) A surface-treated product obtained by treating a member to be treated with the coating agent.

  The silicon oligomer of the present invention is superior in hydrolytic property in the presence of water as compared with conventional silicon oligomers.

  In addition, the method for producing a silicon oligomer of the present invention is a method that does not require separation and purification and operation, and can obtain an oligomer simply and with good reproducibility.

  Furthermore, since the raw material oligomer itself can be dissolved in a solvent containing water, the coating agent containing the silicon oligomer of the present invention is an assembly as a water-soluble coating, and is excellent in handleability.

  Furthermore, when the member to be treated is treated with the coating agent containing the silicon oligomer of the present invention, it is possible to impart functionality such as corrosion resistance and a high friction coefficient to the member to be treated.

上記一般式（I）において、Ｒ_１〜Ｒ_１０はそれぞれ独立して炭素数１〜４のアルキル基またはヒドロキシアルキル基であり、好ましくは炭素数２のアルキル基またはヒドロキシアルキル基であり、より好ましくは炭素数２のヒドロキシアルキル基である。The silicon oligomer of the present invention is a silicon oligomer represented by the following general formula (I).

In the general formula (I), R _{1 to} R ₁₀ are each independently an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, preferably an alkyl group or a hydroxyalkyl group having 2 carbon atoms, and more preferably Is a hydroxyalkyl group having 2 carbon atoms.

上記一般式（II）において、Ａは炭素数２〜４の分岐していてもよいアルキレン基であり、好ましくはエチレン基、プロピレン基、ブチレン基であり、より好ましくはエチレン基である。また、ｌは１〜３の整数であり、好ましくは１である。In the above general formula (I), X _{1 to} X ₃ are each independently represented by the following general formula (II).

In the above general formula (II), A is an alkylene group having 2 to 4 carbon atoms which may be branched, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group. L is an integer of 1 to 3, preferably 1.

  Further, in the above general formula (I), n is 0 or 1, m is an integer of 1 to 3 when n is 0, 1 when n is 1, preferably n is 0, m is 1.

上記一般式（V）において、Ｒ_１５〜Ｒ_２０はそれぞれ独立してエチル基またはヒドロキシエチル基、好ましくは全てがエチル基またはヒドロキシエチル基である。Particularly preferred embodiments of the silicon oligomer of the present invention include those represented by the following general formula (V).

In the general formula (V), R _{15 to} R ₂₀ are each independently an ethyl group or a hydroxyethyl group, preferably all are an ethyl group or a hydroxyethyl group.

で表されるテトラアルコキシシランと、以下の一般式（IV）

で表される２価アルコールを、金属触媒、酸またはアルカリの存在下、好ましくは金属触媒の存在下で反応させることにより得ることができる。また、この反応の際に生成するアルコールを分留しないことにより、重合反応が制御されるので好ましい。なお、従来テトラアルコキシシランの重合反応に用いられる固体樹脂触媒等を用いた場合には、重合反応の制御が困難であるため、上記一般式（Ｉ）で表されるシリコンオリゴマーは得られない。The method for producing the silicon oligomer of the present invention (hereinafter referred to as “the process of the present invention”) is not particularly limited, but for example, the following general formula (III)

A tetraalkoxysilane represented by the following general formula (IV)

Can be obtained by reacting in the presence of a metal catalyst, acid or alkali, preferably in the presence of a metal catalyst. In addition, it is preferable not to fractionate the alcohol produced during this reaction because the polymerization reaction is controlled. When a solid resin catalyst or the like conventionally used for the polymerization reaction of tetraalkoxysilane is used, it is difficult to control the polymerization reaction, and thus the silicon oligomer represented by the general formula (I) cannot be obtained.

In the tetraalkoxysilane represented by the general formula (III), R _{11 to} R ₁₄ are each independently an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, preferably an alkyl group or hydroxy group having 2 carbon atoms. An alkyl group, more preferably a hydroxyalkyl group having 2 carbon atoms. Moreover, the tetraalkoxysilane represented by general formula (III) may use 1 type (s) or 2 or more types.

  In the dihydric alcohol represented by the general formula (IV), B is an alkylene group having 2 to 4 carbon atoms which may be branched, preferably an alkylene group having 2 carbon atoms, and k is 1 It is an integer of -3, Preferably it is 1. Specific examples of the dihydric alcohol represented by the general formula (IV) include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, and triethylene glycol. Among these, ethylene glycol, propylene glycol, and butylene glycol are preferable. . Moreover, the dihydric alcohol represented by general formula (IV) may use 1 type (s) or 2 or more types.

  In the production method of the present invention, the metal catalyst to be present in the above reaction is not particularly limited as long as it contains a metal having a catalytic action, and includes, for example, aluminum, cobalt, titanium, zinc, molybdenum, tin and the like. The thing is mentioned, Preferably the thing containing aluminum, cobalt, and titanium is mentioned. Specific examples of the metal catalyst include aluminum salts such as aluminum chloride, cobalt salts such as cobalt chloride, titanium salts such as titanium chloride, and the like, preferably aluminum chloride. These metal catalysts may be used alone or in combination of two or more. In addition, these metal catalysts are made to exist in the state dissolved in the dihydric alcohol represented by general formula (IV) in the system in the case of the said reaction.

  In the production method of the present invention, examples of the acid present during the reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. These acids are present in the system in the state of being dissolved in the dihydric alcohol represented by the general formula (IV) in the reaction.

  Specifically, in the production method of the present invention, after adding a metal catalyst, an acid or an alkali to the dihydric alcohol represented by the general formula (IV), the mixture is heated to the reaction temperature while stirring. The represented tetraalkoxysilane is added and allowed to react. The reaction temperature is 25 to 150 ° C., preferably 30 to 70 ° C., and the reaction time is 30 minutes to 8 hours, preferably 2 hours to 4 hours. In the reaction, the tetraalkoxysilane represented by the general formula (III) and the dihydric alcohol represented by the general formula (IV) are used in a molar ratio of 4: 1 to 1: 4, preferably 1: 2. It is important to react at ˜1: 4. As a result, the dihydric alcohol represented by the general formula (IV) is taken in between the tetraalkoxysilane and the tetraalkoxysilane, and the distance between the silicon atoms is increased.

The silicon oligomer of the present invention thus obtained can be identified by a known method such as ¹ HNMR, ²⁹ SiNMR, IR, MASS. Specifically, it can be identified by ¹ HNMR and ²⁹ SiNMR.

  The silicon oligomer of the present invention is a polymerizable substance that is polymerized by heating or the like to obtain a polymerizable product. In addition, the silicon oligomer of the present invention has a property of being dissolved in a solvent such as water, isopropyl alcohol, and ethyl cellosolve, and a mixed solvent thereof.

  The silicon oligomer of the present invention can be stably stored even in the presence of water when diluted with a glycol solvent such as polyethylene glycol or ethyl cellosolve. In particular, by using polyethylene glycol 200 to 1000, preferably polyethylene glycol 200, as a glycol solvent, it can be stably stored for a long time even in the presence of moisture.

  In addition, the silicon oligomer of the present invention has the above-described properties, and can be used for applications such as a surface treatment agent in the same manner as a conventionally known silicon oligomer.

  Furthermore, when the silicon oligomer of the present invention is heated as it is, a polymerizable product can be obtained and a flexible film can be formed. Therefore, the silicon oligomer of the present invention is preferably used as a coating agent, particularly a fastening member coating agent, utilizing this property.

  The coating agent containing the silicon oligomer of the present invention (hereinafter referred to as “the coating agent of the present invention”) is not particularly limited as long as it contains the silicon oligomer of the present invention. For example, it can be added to a conventionally known coating agent. One or two or more selected from the group consisting of a resin, a colorant, a friction coefficient modifier, and a film thickener may be contained. Such a coating agent can be prepared by appropriately stirring and mixing the above components.

  The resin used in the coating agent of the present invention is not particularly limited as long as it is soluble or dispersed in the coating agent, and examples thereof include acrylic resins, urethane resins, phenol resins, and epoxy resins. Among these resins, acrylic resins are preferable, methacrylic acid alkyl ester copolymers, colloidal silica / acrylic composites, ethylene / acrylic acid copolymer ammonium salts are more preferable, and methacrylic acid alkyl ester copolymers. Is particularly preferred. These resins can be used alone or in combination of two or more. These resins are blended in the coating agent in an amount of 0.1 to 50%, preferably 1 to 20%.

  The colorant used in the coating agent of the present invention is not particularly limited as long as it is soluble or dispersed in the coating agent, and examples thereof include dye-based colorants and pigment-based colorants. These colorants can be used alone or in combination of two or more. These colorants are blended in the coating agent in an amount of 0.1 to 50%, preferably 1 to 30%.

  Furthermore, the friction coefficient adjusting agent used in the coating agent of the present invention is not particularly limited as long as it is soluble or dispersed in the coating agent. For example, polyolefin compounds such as polyethylene and polypropylene, polytetrafluoroethylene ( PTFE) and fluorine compounds such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). These friction coefficient modifiers can be used alone or in combination of two or more. These friction coefficient adjusting agents are blended in the coating agent in an amount of 0.1 to 10%, preferably 0.5 to 5%.

  Furthermore, the film thickener used in the coating agent of the present invention is not particularly limited as long as it is soluble or dispersible in the coating agent, and examples thereof include colloidal silica and fumed silica. These film thickeners can be used alone or in combination of two or more. These film increasing agents are blended in the coating agent in an amount of 0.1 to 20%, preferably 1 to 10%.

  Furthermore, the present coating agent can be blended with other components such as a functionality-imparting agent in an amount that does not impair the effects of the present invention.

  By treating the member to be treated with the coating agent of the present invention described above, the surface treatment of the member to be treated can be performed.

  Specifically, as the member to be treated, the surface of the member to be treated may be formed of metal and resin, and there is no problem even if the inside is composed of any material. Further, the shape of the member to be processed is not particularly limited.

Examples of the member to be treated that can be treated with the coating agent of the present invention include those in which the surface of the member to be treated is formed by the following (a) to (d), preferably (b).
(A) Magnesium or magnesium alloy (b) Zinc or zinc alloy (c) One type of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium and tin or an alloy consisting of two or more types of the above metals (d ) One type of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine and polyimide, or a synthetic resin alloy comprising two or more of the above resins

  In addition, the treatment of the member to be treated with the coating agent of the present invention may be the same as a conventionally known method for treating the coating agent. If necessary, heating or the like may be performed.

  Specifically, when the member to be treated is immersed in the coating agent of the present invention, for example, a dip and spin method is preferable.

  Moreover, when spraying this invention coating agent on a to-be-processed member specifically, the spray coating method is preferable, for example.

  Furthermore, the heating may be performed at a temperature equal to or higher than the temperature at which the film is formed, for example, 80 ° C. or higher, preferably 100 to 200 ° C.

  Furthermore, the member to be treated may be treated again with the coating agent after heating and heated to form a laminated structure.

  The product subjected to surface treatment with the coating agent of the present invention thus obtained is imparted with corrosion resistance and functionality. Therefore, it can use suitably for uses, such as a fastening member.

  Here, the corrosion resistance refers to corrosion resistance, and the function refers to adjustment of the coefficient of friction. Here, the corrosion resistance means that a salt spray test is performed according to JIS Z 2371, and the white rust generation area is 7% or less, preferably 5% or less, more preferably 3% or less. The friction coefficient adjustment means that variation in the friction coefficient of the coating is suppressed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.

Example 1
Preparation of silicon oligomer:
1.8 g of aluminum chloride hexahydrate was added to 336 g (5.4 mol) of ethylene glycol, and this was heated to 50 ° C. with a mantle heater while stirring, and 564 g of tetraethoxysilane (TEOS) (2 0.7 mol) was mixed and the alcohol produced during the substitution reaction was allowed to react for 2 hours without fractional distillation. The temperature during the reaction was 50 ° C. or lower. In addition, TEOS and ethylene glycol were not mixed before the reaction and two layers were separated, but after the reaction, TEOS was completely reacted, so that a single layer was formed. From this, it was found that the reaction rate of TEOS was 100%.

After the reaction, cooling was performed to obtain a reaction product. ¹ HNMR and ²⁹ SiNMR were measured before and after the reaction. ^{In 1} HNMR, ethanol-derived peaks appeared in the vicinity of 1.1 and 3.5 ppm in the spectrum after completion of the reaction. This ethanol was considered to be produced as a result of a substitution reaction between the ethoxy group of TEOS and ethylene glycol.

In ²⁹ SiNMR, in the spectrum before the reaction, only a single peak derived from TEOS appeared in the vicinity of −82 ppm, but in the spectrum after the reaction, a plurality of peaks appeared in the range of −90 ppm to −80 pm. It was. From this, it was considered that the number of Si in the molecule was 2-4.

The structure of the silicon oligomer determined by NMR is a group represented by the general formula (I) in which R _{1 to} R ₁₀ are ethyl groups, X _{1 to} X ₃ are represented by the general formula (II), and n Is 0 or 1, m is an integer of 1 to 3 when n is 0, is 1 when n is 1, and in general formula (II), A is an ethylene group, and l is 1 It is.

Example 2
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1 except that the amount of ethylene glycol was 83.9 g (1.35 mol).

  Before the reaction, TEOS and ethylene glycol were not mixed, and two layers were separated. After the reaction, unreacted TEOS remained in the supernatant and two layers were separated. From this, it was found that the reaction rate of TEOS was poor.

  However, it was found that the same structure as in Example 1 was obtained although the yield was low because the supernatant was separated and baked to form a film.

Example 3
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1 except that the amount of ethylene glycol was 177.8 g (2.7 mol).

  Before the reaction, TEOS and ethylene glycol were not mixed, and two layers were separated. After the reaction, unreacted TEOS remained in the supernatant and two layers were separated. From this, it was found that the reaction rate of TEOS was poor.

  However, it was found that the same structure as in Example 1 was obtained although the yield was low because the supernatant was separated and baked to form a film.

Example 4
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1 except that the amount of aluminum chloride hexahydrate was 18 g.

  Before the reaction, TEOS and ethylene glycol were not mixed and the two layers were separated, but after the reaction, TEOS was completely reacted, so that a single layer was formed. From this, it was found that the reaction rate of TEOS was 100%.

Example 5
Preparation of silicon oligomer:
A silicon oligomer was prepared in the same manner as in Example 1 except that 1.8 g of aluminum chloride hexahydrate was changed to 0.93 g of cobalt chloride hexahydrate in Example 1.

  Before the reaction, TEOS and ethylene glycol were not mixed and the two layers were separated, but after the reaction, TEOS was completely reacted, so that a single layer was formed. From this, it was found that the reaction rate of TEOS was 100%.

Example 6
Preparation of silicon oligomer:
A silicon oligomer was prepared in the same manner as in Example 1, except that 1.8 g of aluminum chloride hexahydrate was changed to 0.64 g of titanium trichloride.

  Before the reaction, TEOS and ethylene glycol were not mixed and the two layers were separated, but after the reaction, TEOS was completely reacted, so that a single layer was formed. From this, it was found that the reaction rate of TEOS was 100%.

Example 7
Preparation of silicon oligomer:
A silicon oligomer was prepared in the same manner as in Example 1, except that 1.8 g of aluminum chloride hexahydrate was changed to 0.8 g of hydrochloric acid.

  Before the reaction, TEOS and ethylene glycol were not mixed and the two layers were separated, but after the reaction, TEOS was completely reacted, so that a single layer was formed. From this, it was found that the reaction rate of TEOS was 100%.

Comparative Example 1
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1 except that ethylene glycol was changed to 336 g of water.

  Before the reaction, TEOS and ethylene glycol were not mixed and the two layers were separated, but after the reaction, TEOS was completely reacted, so that a single layer was formed. From this, it was found that the reaction rate of TEOS was 100%.

Test example 1
Stability test:
Diluted solution diluted with ethyl cellosolve so that the silicon oligomer prepared in Examples 1, 4 to 7 or Comparative Example 1 becomes 10%, or various model numbers so that the silicon oligomer prepared in Example 1 becomes 10%. A diluted solution diluted with polyethylene glycol was prepared. Further, each of these diluted solutions diluted twice with water was used as a test solution (silicon oligomer was 5%). Each of these test solutions was placed in a glass container and stored at room temperature. After storage, it was observed daily until changes occurred. The observation results are shown in Table 1.

  It was found that the silicon oligomer of the present invention is superior in liquid stability as compared with oligomers obtained from general hydrolysis of TEOS. It has also been found that the stability is further improved by diluting the silicon oligomer of the present invention with a glycol solvent.

Test example 2
Film formation test:
Diluted solution diluted with ethyl cellosolve so that the silicon oligomer prepared in Examples 1, 4 to 7 or Comparative Example 1 becomes 10%, or various model numbers so that the silicon oligomer prepared in Example 1 becomes 10%. Diluted solutions diluted with polyethylene glycol were applied to known M8 bolts that had been subjected to known trivalent chromium chemical conversion treatment after galvanizing, and each was fired at 180 ° C. for 20 minutes. After firing, the appearance (film formability) of the obtained film was freely evaluated. The results are shown in Table 2.

  It was confirmed that the silicon oligomer of the present invention was excellent in film formability as compared with the oligomer obtained from the general hydrolysis of TEOS.

Test example 3
Corrosion resistance test:
Commercially available bolts were galvanized and then subjected to chemical conversion treatment (Trivalent 1200: manufactured by JCU). The bolt is diluted with ethyl cellosolve so that the silicon oligomer prepared in Examples 1, 4 to 7 or Comparative Example 1 becomes 10%, or the silicon oligomer prepared in Example 1 becomes 10%. After immersing and centrifuging in diluted solutions diluted with various types of polyethylene glycol, each was fired at 180 ° C. for 20 minutes. These bolts were subjected to a salt spray test for 240 hours. The salt spray test was performed according to JIS Z 2371. After the salt spray test, the area where white rust was generated on the bolt was visually measured. The results are shown in Table 3.

  Corrosion from the cracks that occurred was observed in the oligomeric polymer obtained from the general hydrolysis of TEOS. On the other hand, the polymer of the silicon oligomer of the present invention was found to have a high antirust effect. Moreover, it turned out that high corrosion resistance is acquired, so that the density | concentration of the catalyst (aluminum chloride) added in the case of manufacture of the silicon oligomer of this invention is high.

Example 8
Preparation of coating agent:
The silicon oligomer prepared in Example 1 was dissolved in a methacrylic acid alkyl ester copolymer (Nigazole PK8012P: manufactured by Nippon Carbide Industries Co., Ltd.) so as to be 3% to prepare a coating agent.

Example 9
Preparation of coating agent:
The silicon oligomer prepared in Example 1 was dissolved in a colloidal silica / acrylic composite (New Coat PM-3101-01: manufactured by Shin-Nakamura Chemical Co., Ltd.) so as to be 3% to prepare a coating agent.

Example 10
Preparation of coating agent:
The silicon oligomer prepared in Example 1 was dissolved in ethylene / acrylic acid copolymer ammonium salt (Zyxen N: manufactured by Sumitomo Seika Co., Ltd.) so as to be 3% to prepare a coating agent.

Test example 4
Stability test:
The coating agent prepared in Examples 8 to 10 was placed in a glass container and stored at room temperature. After storage, it was observed daily until changes occurred. The observation results are shown in Table 4.

  The silicon oligomer prepared in Example 1 was found to be stable in each resin of Examples 8-10.

Example 11
Preparation of coating agent:
In water, the silicon oligomer prepared in Example 1 was 3%, the methacrylic acid alkyl ester copolymer (Nigazole PK8012P: manufactured by Nippon Carbide Industries) was 7%, polyethylene glycol 200 was 1%, and isopropyl alcohol was 20%. Thus, a coating agent was prepared by dissolution.

Example 12
Preparation of coating agent:
In water, 3% of the silicon oligomer prepared in Example 1, 7% of colloidal silica / acrylic composite (New Coat PM-3101-01, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1% of polyethylene glycol 200 and isopropyl alcohol A coating agent was prepared by dissolving to 20%.

Example 13
Preparation of coating agent:
In water, 3% of the silicon oligomer prepared in Example 1, 7% of ethylene / acrylic acid copolymer ammonium salt (Zyxen N: manufactured by Sumitomo Seika), 1% of polyethylene glycol 200 and 20% of isopropyl alcohol The coating agent was prepared by dissolving.

Test example 5
Film formation test:
Each of the coating agents prepared in Examples 11 to 13 was applied to a test piece (1 dm ² ) of SUS304 and baked at 180 ° C. for 20 minutes. After firing, the appearance (film formability) of the obtained film was freely evaluated. For comparison, a similar test was performed using a coating agent containing only a methacrylic acid alkyl ester copolymer, which is a resin component of the coating agent. The results are shown in Table 5.

  In the case of the coating agent containing only the resin component, cracks were observed at the fractured part during film formation, but in the coating agent used in combination with the resin component and the silicon oligomer of the present invention, the physical properties of the coating film were improved.

Test example 6
Fastening member evaluation:
(1) Coating Zinc plating was performed on a commercially available flanged bolt, and then chemical conversion treatment (Trivalent 1200: manufactured by JCU) was performed. This bolt was immersed in the coating agent prepared in Example 11, centrifuged, and then fired at 180 ° C. for 20 minutes. For comparison, a bolt without a coating agent and a bolt coated only with a methacrylic acid alkyl ester copolymer which is a resin component of the coating agent prepared in Example 11 were prepared.

(2) Corrosion resistance test The bolt obtained in (1) above was subjected to a salt spray test and its evaluation in the same manner as in Test Example 3. The results are shown in Table 6.

(3) Friction coefficient measurement About the bolt obtained by said (1), the friction coefficient was evaluated on the conditions shown below using the friction coefficient measuring apparatus (made by Iwata Iron Works). The results are shown in Table 6.

<Friction coefficient measurement conditions>
Test screw: Bolt with flange Test speed: 3-10rpm
Tightening method: Specified axial force method Measurement total torque: 50 to 90 N · m
Measuring axial force: 20-30kN (designated axial force stop)
Measurement screw torque: Not specified Motor output: 1.5kW

  The coating agent without the coating agent and the resin component alone has a markedly poor corrosion resistance, but the coating agent used in combination with the resin component and the silicon oligomer of the present invention shows a significant improvement in corrosion resistance. Further, the coating agent used in combination with the resin component and the silicon oligomer of the present invention has suppressed variation in the friction coefficient.

Test example 7
Extendability confirmation test:
Commercially available flanged bolts were galvanized and then subjected to chemical conversion treatment (Trivalent 1200: manufactured by JCU). The bolt was diluted with ethyl cellosolve so that the silicon oligomer prepared in Example 4 had a solid content of 20% or the coating agent prepared in Example 11, and each was immersed and centrifuged. Baked at 20 ° C. for 20 minutes. These bolts were subjected to a tightening test using the friction coefficient measuring apparatus (manufactured by Iwata Iron Works) used in Test Example 6 (3), and the coating state of the contact portion between the flange and the bearing surface after tightening was visually evaluated. For comparison, a similar test was performed using a coating agent (JN1710: manufactured by JCU Nanomate Co., Ltd.) containing a silicon oligomer (polysiloxane) having a short interelectrode distance between silicon structures. The results are shown in Table 7.

  In the coating agent containing a silicon oligomer having a short inter-electrode distance between silicon structures, the coating film was crushed during tightening. On the other hand, it was found that the coating film was not crushed by using the coating agents of Example 4 and Example 11.

Example 12
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1 except that ethylene glycol was changed to 810.9 g (5.4 mol) of triethylene glycol. Regarding the obtained silicon oligomer, TEOS and triethylene glycol were not mixed before the reaction and two layers were separated, but after the reaction, TEOS was completely reacted, so that it became a single layer. From this, it was found that the reaction rate of TEOS was 100%. Moreover, since it formed into a film by baking, it was thought that it was a polymerizable product like Example 1.

The structure of the obtained silicon oligomer is that in general formula (I), R _{1 to} R ₁₀ are ethyl groups, X _{1 to} X ₃ are groups represented by general formula (II), and n is 0 or 1 and m is an integer of 1 to 3 when n is 0, 1 when n is 1, and in general formula (II), A is an ethylene group and l is 3.

Example 13
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as Example 1 except that ethylene glycol was changed to 486.6 g (5.4 mol) of 1,3-butylene glycol. About the obtained silicon oligomer, TEOS and 1,3-butylene glycol were not mixed before the reaction, and two layers were separated. However, after the reaction, TEOS was completely reacted to form a single layer. From this, it was found that the reaction rate of TEOS was 100%. Moreover, since it formed into a film by baking, it was thought that it was a polymerizable product similarly to Example 1. FIG.

The structure of the obtained silicon oligomer is that in general formula (I), R _{1 to} R ₁₀ are ethyl groups, X _{1 to} X ₃ are groups represented by general formula (II), and n is 0 or 1 and m is an integer of 1 to 3 when n is 0, 1 when n is 1, and in general formula (II), A is a methylpropylene group and l is 1. .

Example 14
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1, except that tetraethoxysilane was changed to 411.1 g (2.7 mol) of tetramethoxysilane. About the obtained silicon oligomer, tetramethoxysilane and ethylene glycol were not mixed before the reaction, and two layers were separated. However, after the reaction, TEOS was completely reacted to form a single layer. From this, it was found that the reaction rate of tetramethoxysilane was 100%. Moreover, since it formed into a film by baking, it was thought that it was a polymerizable product like Example 1.

The structure of the obtained silicon oligomer is that in general formula (I), R _{1 to} R ₁₀ are methyl groups, X _{1 to} X ₃ are groups represented by general formula (II), and n is 0 or 1 and m is an integer of 1 to 3 when n is 0, 1 when n is 1, and A is an ethylene group and 1 is 1 in the general formula (II).

Example 15
Preparation of silicon oligomer:
In Example 1, a silicon oligomer was prepared in the same manner as in Example 1 except that tetrabutoxysilane was changed to 865.5 g (2.7 mol) of tetrabutoxysilane. Before the reaction, the resulting silicon oligomer was not mixed with tetrabutoxysilane and ethylene glycol, and was separated into two layers, but after the reaction, TEOS was completely reacted to form a single layer. From this, it was found that the reaction rate of tetrabutoxysilane was 100%. Moreover, since it formed into a film by baking, it was thought that it was a polymerizable product like Example 1.

The structure of the obtained silicon oligomer is that in general formula (I), R _{1 to} R ₁₀ are butyl groups, X _{1 to} X ₃ are groups represented by general formula (II), and n is 0 or 1 and m is an integer of 1 to 3 when n is 0, 1 when n is 1, and A is an ethylene group and 1 is 1 in the general formula (II).

  The silicon oligomer of the present invention can be used for applications such as a surface treating agent as in the case of conventionally known silicon oligomers.

  In particular, when the silicon oligomer of the present invention is used as a coating agent, a flexible film can be formed, so that it can be suitably used for coating fastening members and the like.

Claims (20)

The following general formula (I)

(However, R _{1 to} R ₁₀ are each independently an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and X _{1 to} X ₃ are each independently the following general formula (II):

(However, A is an alkylene group having 2 to 4 carbon atoms which may be branched, and l is an integer of 1 to 3)
And n is 0 or 1, m is an integer of 1 to 3 when n is 0, and 1 when n is 1)
The coating agent characterized by including the silicon oligomer represented by these.   Furthermore, the coating agent of Claim 1 which contains 1 type (s) or 2 or more types chosen from the group which consists of resin, a coloring agent, a friction coefficient modifier, and a film thickener.   The coating agent according to claim 2, wherein the resin is one or more selected from the group consisting of an acrylic resin, a urethane resin, a phenol resin, and an epoxy resin.   The coating agent according to claim 2, wherein the colorant is one or more selected from the group consisting of a dye-based colorant and a pigment-based colorant.   The coating agent according to claim 2, wherein the friction coefficient adjusting agent is one or more selected from polyolefin compounds and fluorine compounds.   The coating agent according to claim 2, wherein the film-increasing agent is one or more selected from the group consisting of colloidal silica and fumed silica. Silicon oligomers have the following general formula (III)

_{(Wherein, R} 11 _{~ 14} is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms each independently)
And a tetraalkoxysilane represented by the following general formula (IV)

(However, B is a C2-C4 alkylene group which may be branched, and k is an integer of 1-3.)
The coating agent according to claim 1, which is obtained by reacting a dihydric alcohol represented by the formula (I) in the presence of a metal catalyst.   The coating agent according to claim 7, wherein the metal catalyst contains one or more selected from aluminum, cobalt, titanium, zinc, molybdenum and tin.   The coating agent according to claim 7, wherein the dihydric alcohol represented by the general formula (IV) is one or more selected from ethylene glycol, propylene glycol and butylene glycol.   The coating agent according to claim 7, wherein the molar ratio of the tetraalkoxysilane represented by the general formula (III) and the dihydric alcohol represented by the general formula (IV) is 4: 1 to 1: 4.   A surface treatment method for treating a member to be treated with the coating agent according to claim 1.   The surface treatment method according to claim 11, wherein the surface of the member to be treated is magnesium or a magnesium alloy.   The surface treatment method according to claim 11, wherein the surface of the member to be treated is zinc or a zinc alloy.   The surface treatment method according to claim 11, wherein the surface of the member to be treated is one type of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium, and tin, or an alloy containing two or more types of the metal.   The surface of the member to be treated is one type of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine and polyimide, or a synthetic resin alloy consisting of two or more types of the resins. 11. The surface treatment method according to 11.   The surface treatment product obtained by processing a to-be-processed member with the coating agent in any one of Claims 1-10.   The surface-treated product according to claim 16, wherein the surface of the member to be treated is magnesium or a magnesium alloy.   The surface-treated product according to claim 16, wherein the surface of the member to be treated is zinc or a zinc alloy.   The surface-treated product according to claim 16, wherein the surface of the member to be treated is one kind of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium, and tin, or an alloy composed of two or more kinds of the metals.   The surface of the member to be treated is one type of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine and polyimide, or a synthetic resin alloy consisting of two or more types of the resins. 16. The surface treatment product according to 16.