JP3189373B2 - Method for producing polysiloxane composite polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polysiloxane composite polymer.

[0002]

2. Description of the Related Art In recent years, as a material having the advantages of inorganic materials such as hardness, chemical resistance and heat resistance, and the advantages of organic polymers such as flexibility, and at the same time complementing the disadvantages of both. Attention has been focused on inorganic-organic composites.

[0003] The organic polymer of acrylic acid polymer or methacrylic acid polymer as an example (in conjunction hereinafter (meth) referred acrylic acid polymer) is usually water soluble polymers, hydrophilic polymers, such as the water-absorbing polymer Although it is a useful material, it is unsuitable for applications requiring hardness and some degree of water resistance.

[0004] Organosilanes such as tetramethoxysilane and tetraethoxysilane, hydrolysates thereof and polycondensates thereof produce silica glass by a sol-gel method. Is known to be brittle.

In light of the purpose of the inorganic-organic composite, when an inorganic-organic composite is attempted simply by using a mixture of poly (meth) acrylic acid and the above-mentioned organosilanes, poly (meth) No reaction occurs between the carboxyl group of the acrylic acid and the silanol group of the organosilanes, and the mixture remains as a mere mixture without a chemical bond. Therefore, the compatibility of both components is poor, the occurrence of phase separation, the opacity of the film,
There are disadvantages such as poor water resistance. Also, mixtures of poly (meth) acrylic acid and colloidal silica have similar disadvantages.

[0006] Polymer Preprints, J
apan, Vol. 39, no. 3395 (1990)
Describes an attempt to form a composite of polyacrylic acid and tetraethoxysilane, and describes a porous gel. However, there is no teaching or suggestion for chemically bonding polyacrylic acid and tetraethoxysilane.

[0007]

SUMMARY OF THE INVENTION The present invention provides a composite of a (meth) acrylic acid polymer and an organosilane to provide excellent hardness, gloss, transparency, adhesion, solvent resistance, and ( An object of the present invention is to provide a method for producing a polysiloxane composite polymer having good performance such as improved water resistance as compared with a (meth) acrylic acid polymer.

In view of the problems in the prior art, the present inventor has provided a (meth) acrylic acid polymer-polysiloxane composite polymer (hereinafter, referred to as a polysiloxane composite polymer) capable of exhibiting excellent various performances. Diligent research was conducted. As a result, they have surprisingly found that the above problems can be completely solved for the first time by complexing a (meth) acrylic acid polymer with an organosilane via a specific binder.

[0009] That is, the present invention provides a sol-gel method.
In producing the siloxane composite polymer, (A) selected from the group consisting of organosilanes having no amino group and having 1 to 4 alkoxy groups, hydrolysates thereof and polycondensates thereof Complexing at least one kind with (B) a (meth) acrylic acid polymer in the presence of (C) an organoalkoxysilane having an amino group ;
The present invention relates to a method for producing a characteristic polysiloxane composite polymer .

According to the present invention, the silanol group derived from the component (A) reacts with the alkoxysilyl group in the component (C), and further the amino group in the component (C) and the (B) ) An ionic bond occurs with the carboxyl group in the component. As a result, the component (A) and the component (B) are compounded by the chemical bond via the component (C), so that the resulting complex does not phase-separate into the component (A) and the component (B). Moreover, when the complex is heated, an amide bond is generated by a dehydration reaction between the amino group in the component (C) and the carboxyl group in the component (B), and a bond stronger than the ionic bond is generated. .

The component (A) used in the present invention includes, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , N-
Propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, dimethyldimethoxysilane,
Examples include organosilanes such as dimethyldiethoxysilane and diethyldimethoxysilane, hydrolysates of the organosilanes, and polycondensates thereof, and these can be used alone or in combination of two or more. Of these, preferred are tetramethoxysilane, tetraethoxysilane, hydrolysates thereof and polycondensates thereof. The component (A) may be used in combination with alkoxides of various metals such as titanium and aluminum. The component (A) can be used by dissolving it in water and / or an organic solvent, if necessary.

[0012] As component (B) used in the present invention, such as polyacrylic acid, polymethyl although other acrylic acid is preferred, without departing from the object of the present invention, acrylic acid as required, co and meta acrylic acid A copolymer with a polymerizable monomer may be used.

As the component (C) used in the present invention, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-
3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, trimethoxysilylpropyldiethylenetriamine, triethoxysilylpropyldiethylenetriamine, N-
Various known compounds such as (2-aminoethyl) aminopropylmethyldimethoxysilane, N- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane are exemplified. I can do it. Preferably, they are 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. These may be used alone or in combination of two or more as appropriate. If necessary, a silane coupling agent having no amino group can be used in combination.

In order to produce the polysiloxane composite polymer of the present invention, the component (A), the component (C) and the component (B) previously diluted in water are mixed at a predetermined ratio. At the time of mixing, if necessary, water and / or a hydrophilic solvent such as methanol or ethanol may be added to lower the viscosity. Thereafter, a normal sol-gel method may be adopted. For example, a uniform solution can be obtained by hydrolyzing the alkoxysilyl group in the mixture at 50 ° C. for 5 hours to 1 day. This solution is applied onto a suitable substrate (such as glass) and the coating film is heated and cured at 80 to 200 ° C. to obtain a coating film having high hardness. Further, the solution can be poured into an appropriate container (such as Teflon), air-dried for about one day, and then heat-cured at 80 to 200 ° C. to form a high-hardness molding material. Further, after the porous substrate is impregnated with the solution, heating may be performed.

The mixing ratio of the components (A) and (B) is usually 10 to 1000 parts by weight, preferably 50 to 500 parts by weight of the component (B) per 100 parts by weight of the component (A).
Parts by weight. The amount of the component (C) to be used is generally 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the component (B).

The polysiloxane composite polymer obtained by the method of the present invention has the advantages of an inorganic material and an organic material. Can be used for applications such as anti-condensation agents. In addition, the polysiloxane composite polymer can be used as a transparent polymer having a function of absorbing and releasing moisture because of maintaining appropriate hydrophilicity.

[0017]

According to the method of the present invention, the hardness, gloss,
A great effect is obtained that a polysiloxane composite polymer having excellent transparency, adhesion, and solvent resistance and having appropriate water resistance can be obtained relatively inexpensively.

[0018]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 A reaction vessel was charged with 100 g of an aqueous solution of polyacrylic acid (solid content 15%, viscosity 40,000 cps), ethanol 30 g, tetraethoxysilane 15 g and aminopropyltriethoxysilane 0.75 g while stirring.
Stirring was continued at 5 ° C. for 5 hours to obtain a uniform transparent solution.

Example 2 100 g of the above aqueous solution of polyacrylic acid, 30 g of ethanol, 7.5 g of tetraethoxysilane and 0.75 g of aminopropyltriethoxysilane were charged into a reaction vessel with stirring, and stirring was continued at 50 ° C. for 5 hours. This gave a homogeneous clear solution.

Example 3 100 g of the above-mentioned aqueous solution of polyacrylic acid, 30 g of ethanol, 30 g of tetraethoxysilane and 0.75 g of aminopropyltriethoxysilane were charged into a reaction vessel with stirring, and stirring was continued at 50 ° C. for 5 hours. A homogeneous clear solution was obtained.

Example 4 100 g of the above-mentioned aqueous solution of polyacrylic acid, 30 g of ethanol, 15 g of tetraethoxysilane and 0.375 g of aminopropyltriethoxysilane were charged into a reaction vessel with stirring, and stirring was continued at 50 ° C. for 5 hours. A homogeneous clear solution was obtained.

Example 5 In Example 1, the amount of tetraethoxysilane was changed to 15 g.
Example 1 except that 11 g of tetramethoxysilane was used.
The same operation as described above was performed to obtain a uniform transparent solution.

Example 6 The procedure of Example 1 was repeated, except that 0.71 g of aminopropyltriethoxysilane was used and 0.61 g of aminopropyltrimethoxysilane was used to obtain a uniform transparent solution. .

Comparative Example 1 The same operation as in Example 1 was carried out without adding aminopropyltriethoxysilane to obtain a polyacrylic acid-tetraethoxysilane hydrolyzed solution. This solution was heterogeneous and cloudy. Was.

Comparative Example 2 In a reaction vessel, 100 g of the above-mentioned aqueous solution of polyacrylic acid and acidic colloidal silica (solid content: 20%, trade name: Adelite AT)
-20Q, 22 g of Asahi Denka Kogyo Co., Ltd.) to obtain a slightly turbid solution.

Comparative Example 3 Only a polyacrylic acid (solid content: 15%) was used as a test solution.

(Preparation of Coating Film) The solutions of Examples 1 to 6 and Comparative Examples 1 to 3 were applied to an applicator (3MI
Each of them was applied to a glass plate using L). Then, in a circulating air dryer, 30 minutes at 80 ° C and 30 minutes at 100 ° C.
For 30 minutes at 150 ° C. and 30 minutes at 200 ° C. to prepare a film on a glass plate. After conditioning for one day at room temperature, the state of the film, hardness and water resistance were evaluated.

(Performance test of coating film) Film state Evaluated by visual observation ○ ---- Transparent film × ---- Turbidity or whitening Pencil hardness According to JIS K 5400 6.14 Water-resistant coated Glass plate in water 1
The state of the film after day immersion was evaluated by visual observation. ○ ---- As a transparent film × ---- Turbidity, whitening or swelling These results are shown in Table 1. In addition, the stability of each solution (1
Months) are shown in Table 1.

(Preparation of Test Pieces for Measuring Water Absorption and Release Properties) 3 g of each of the solutions of Examples 1 to 6 and Comparative Examples 1 to 3 was poured into a boat type (10 cm ² ) made of Teflon glass cloth, and 1 g at room temperature. Sun dried naturally. afterwards,
In a circulating air dryer, 30 minutes at 80 ° C, 30 minutes at 100 ° C,
The test piece was prepared by heating and heating at 150 ° C. for 30 minutes and at 200 ° C. for 30 minutes. After humidity control at room temperature for one day, the moisture absorption / release properties were evaluated.

(Moisture absorption / release test) The weight of a test piece is weighed, and its value is defined as M ₁ . After immersion in water for 1 day, lightly wipe the water droplets with filter paper and set the weight to M ₂ . Thereafter, the weight after one day at room temperature is defined as M ₃ . Further in the same manner, the weight after 1 day immersion and M ₄ in water, then the M ₅ weight after standing at room temperature for one day. Water absorption capacity _{(M 2 / M 1, M} 3 / M 1, M 4 / M 1, M 5 / M 1)
Table 2 shows the results of the measurements.

(Coat for measuring moisture absorption / release properties on glass plate)
Preparation of coating film) The solutions of Examples 1 to 6 were applied on a glass plate (200 cm ² ) with a bar coater (RDS12).
, Respectively. Then, in the circulating dryer,
30 minutes at 80 ° C, 30 minutes at 100 ° C, 30 minutes at 150 ° C
And heating at 200 ° C. for 30 minutes to prepare a film on a glass plate. After humidity control at room temperature for one day, the moisture absorption / release properties were evaluated.

The weight of the glass plate is defined as G _1, and the weight of the glass plate after one day of humidity control after forming the film is defined as G ₂ . After immersing the glass plate in water for 1 day, lightly wipe the water drop with filter paper,
The weight of the glass plate at that time and G _3. Thereafter, the weight of the glass plates after standing at room temperature for one day and G _4. The water absorption ratio is (G ₃ −G ₁ ) / (G ₂ −G ₁ ) = Ga,
(G ₄ −G ₁ ) / (G ₂ −G ₁ ) = Gr Table 3 shows the results.

[0034]

[Table 1]

[0035]

[Table 2] In Comparative Examples 1 to 3, when water was absorbed, it did not return to the original shape, but became a hydrogel, and the evaluation of water absorption / release properties could not be performed.

[0036]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 133/02 C09D 183/08 183/08 C08K 5/54

Claims (3)

(57) [Claims] 1. A polysiloxane composite weight obtained by a sol-gel method.
Upon producing coalescence, at least one member selected from the group consisting of (A) organosilanes having and one to four alkoxy groups having no amino group, a hydrolyzate thereof and these polycondensates (B) A polysilo compound which is compounded with a (meth) acrylic acid polymer in the presence of (C) an organoalkoxysilane having an amino group.
A method for producing a xanse composite polymer. Wherein said (B) the preparation of a composite polymer of claim 1 wherein component is an acrylic acid polymer. 3. The production of a composite polymer according to claim 1, wherein water and / or a hydrophilic solvent is used at the time of the composite .
Construction method .