JP3022117B2 - One-part curable polysiloxane resin compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-part curable polysiloxane resin compound which can impart excellent surface properties to various films, films and other resin molded products.

[0002]

2. Description of the Related Art The surface of resin molded products such as various films or various coatings is required to be excellent in stain resistance, water resistance, abrasion resistance and adhesion resistance, and in some applications, low surface friction. Coefficients are required.

[0003] In response to such demands, a method of adding a lubricant such as silicone oil, wax or fatty acid which gives lubricity and water repellency to a resin molded product, or a method of applying a silicone or fluorine resin is used. And so on. According to this method, a certain purpose can be achieved, but the lubricant added to the molded product bleeds out to the surface of the molded product with time, causing various problems. It is limited by the amount added, and the desired performance cannot be sufficiently exhibited. As a method for solving the above-mentioned disadvantages, a method using a resin having a low friction coefficient, for example, a polyurethane resin or an acrylic resin having a siloxane bond in a molecule has been proposed.

[0004]

[Problems to be solved by the invention]
Most of these resins are thermosetting resins using various curing agents, and require a heating step for curing when forming a film.
There is a problem that it is complicated. Furthermore, although the formed films have a high melting point, if the curing reaction is insufficient, problems due to poor curing such as solvent resistance, adhesion to a substrate, and heat resistance are likely to occur. Accordingly, an object of the present invention is to provide a one-part curable polysiloxane resin compound having a simple film forming process and excellent performance.

[0005]

The above object is achieved by the present invention described below. That is, the present invention is a compound containing a resin having a siloxane segment, polysiloxane compound the resin has a reactive organic functional group and y
A one-part curable product, which is a reaction product of a silane coupling agent having a reactive organic functional group other than a cyanate group and an organic polyisocyanate, comprising a resin having at least one free isocyanate group. Polysiloxane resin compound.

[0006]

The film-forming material is a reaction product of a polysiloxane compound having a reactive organic functional group, a silane coupling agent having a reactive organic functional group, and an organic polyisocyanate, wherein at least one free isocyanate is used. By forming the film-forming material from a resin having a group, the film-forming material is crosslinked by moisture or moisture in the air, so that one-component curing becomes possible, and the process of forming the film layer is simplified. Further, due to the presence of the free isocyanate group and the hydrolyzable silyl group, the adhesion of the coating layer to the base sheet is improved, and a coating layer having excellent performance is formed.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. Preferred examples of the reactive organic functional group-containing polysiloxane compound used in the present invention include the following compounds.

(1) Amino-modified polysiloxane compound

[0009]

(2) Epoxy-modified polysiloxane compound The above epoxy compound can be used by reacting it with a polyol, polyamide, polycarboxylic acid or the like so as to have a terminal active hydrogen.

(3) Alcohol-modified polysiloxane compound

[0012]

(4) Mercapto-modified polysiloxane compound

(5) Carboxyl-modified polysiloxane compound

The polysiloxane compounds having a reactive organic functional group listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these examples. Therefore, not only the compounds exemplified above, but also other compounds that are currently commercially available and easily obtainable from the market can be used in the present invention.

The silane coupling agent having a reactive organic functional group other than the isocyanate group used in the present invention includes, for example, compounds of the following general formula. (Y is, for example, a group capable of reacting with an isocyanate group such as an amino group, an epoxy group, a hydroxyl group, a thiol group and the like, particularly preferably an amino group, a thiol group and a hydroxyl group.
¹ , R ² , X, m and n are as defined above. Preferred specific examples of the silane coupling agent having a reactive organic functional group are as follows.

[0017]

[0018] The silane coupling agents listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these examples. Therefore, not only the above-listed compounds but also other compounds that are currently commercially available and easily available from the market can be used in the present invention.

As the organic polyisocyanate to be reacted with the above-mentioned polysiloxane compound and silane coupling agent used in the present invention, any known organic polyisocyanate can be used. 4-diisocyanate 4-methoxy-1,3-phenylene diisocyanate 4-isopropyl-1,3-phenylene diisocyanate 4-chloro-1,3-phenylene diisocyanate 4-butoxy-1,3-phenylene diisocyanate 2,4-diisocyanate-diphenyl ether Methylene diisocyanate 4,4-methylenebis (phenyl isocyanate) judylene diisocyanate 1,5-naphthalenedi isocyanate benzidine diisocyanate o-nitrobenzidine diisocyanate 4,4-diisocyanate dibenzyl 1,4-tetramethylene diisocyanate 1,6-tetramethylene diisocyanate 1,10-decamethylene diisocyanate 1,4-cyclohexylene diisocyanate xylylene diisocyanate 4,4-methylene bis (cyclohexyl isocyanate) 1,5 -Tetrahydronaphthalenediisocyanate and the like.

Further, adducts of these organic polyisocyanates with other compounds, for example, those having the following structural formulas, are not limited thereto.

[0021] Urethane prepolymers obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines so as to be terminal isocyanates can also be used in the present invention.

The reaction product used in the present invention comprises a polysiloxane compound having a reactive organic functional group as described above.
A silane coupling agent having a reactive organic functional group other than an isocyanate group and the organic polyisocyanate as described above are reacted with an excess of one or more isocyanate groups in one molecule of the reactive organic functional group and the isocyanate group. The reaction is carried out at a temperature of about 0 to 150 ° C., preferably 20 to 80 ° C. for about 10 to 4 hours in the presence or absence of a general urethane catalyst in a solvent-free or organic solvent at a functional group ratio of Can be easily obtained.

The reaction product used in the film-forming material of the present invention can be used alone. However, in order to improve the suitability for coating a substrate sheet or the like, the film formability, and the like,
Conventionally known various resins can be mixed and used.
As these various resins, those capable of chemically reacting with the free isocyanate of the reaction product of the present invention are preferable, but those having no reactivity can also be used in the present invention.

These resins include acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin,
Polyvinyl chloride resin, cellulose resin, epoxy resin,
Polyvinyl butyral resin, alkyd resin, modified cellulose resin, fluorine resin, polyamide resin, or the like can be used. In addition, resins obtained by modifying various resins with silicone or fluorine can also be used. When these various resins are used in combination, the amount used is 0.1% by weight to 100% by weight based on the solid content of the above reaction product.

The film-forming material of the present invention comprises water in the air,
By contacting with water or steam, the hydrolyzable silyl group in the reaction product undergoes a crosslinking reaction and cures, and also reacts with free isocyanate to cure, so special heating equipment and treatment for curing are required. do not need.

In the present invention, in order to promote this silanol condensation, it is preferable to add a catalyst to the film-forming material. Such catalysts generally include alkyl titanates,
Preference is given to tin octylates, carboxylate salts such as dibutyltin dilaurate, amino salts such as dibutylamine-2-ethylhexoate, and other acidic and basic catalysts. The amount of the reaction product to be used is 0.1 to 0.1%.
The range of 0001% by weight to 10% by weight is preferred. Also, some free isocyanate groups and hydrolyzable silyl groups,
The interaction with the interface of the base sheet improves the adhesiveness of the coating layer to the base sheet, and the polysiloxane portion is oriented on the surface of the coating layer. It is possible to provide a surface property having excellent performances such as water resistance and chemical resistance.

[0027]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In addition, "part" or "%" in the text
Unless otherwise specified, the values are based on weight. Reference Example 1 Adduct of hexamethylene diisocyanate with water [Duranate 24A-100, manufactured by Asahi Kasei Corporation, NCO% =
23.5%] 150 parts and ethyl acetate 100 parts at 80 ° C
While stirring well, polydimethylsiloxane having a terminal hydroxyl group having the above structure (molecular weight 2,200)
12 parts were gradually dropped and reacted for 4 hours.

Thereafter, the mixture is cooled to 40 ° C. and stirred well.
56 parts of 3-aminopropyltriethoxysilane was gradually dropped therein to cause a reaction to obtain a reaction product (1).
According to the infrared absorption spectrum of the obtained reaction product (1), absorption by a free isocyanate group was observed at 2,270 cm ⁻¹ , and an absorption band based on a —SiO— group was found at 1,090 cm ^−1. Was shown. Further, when the free isocyanate groups of the reaction product (1) were quantified, the theoretical value was 11.1%, whereas the actually measured value was 10.3% (as pure content). Finally, ethyl acetate was added to obtain a resin solution (A) of a reference example having a solid content of 50%.

Reference Example 2 1 mole of trimethylolpropane and 3 moles of toluene
Adduct with 2,4-diisocyanate (Coronate L,
200 parts of NCO% = 13.0%, solid content 75%, manufactured by Nippon Polyurethane Co., Ltd.) 200 parts of ethyl acetate and 100 parts of ethyl acetate were thoroughly stirred at 80 ° C., and the polydimethyl group having hydroxyl groups at both ends having the above structure was added thereto. Siloxane (molecular weight 3,200) 1
Two parts were gradually dropped to react.

Thereafter, the mixture is cooled to 40 ° C. and stirred well.
62 parts of N-phenyl-γ-aminopropyltriethoxysilane was gradually dropped therein and reacted to obtain a reaction product (2). According to the infrared absorption spectrum of the obtained reaction product (2), absorption due to a free isocyanate group was observed at 2,270 cm ⁻¹ , and −1.090 cm ⁻¹ .
The absorption band based on the SiO- group was shown. In addition, when the free isocyanate groups of this reaction product (2) were quantified, the theoretical value was 6.9%, whereas the actually measured value was 5.1% (as pure content). Finally, ethyl acetate was added to obtain a resin solution (B) of a reference example having a solid content of 50%.

Reference Example 3 Trimer of hexamethylene diisocyanate (Coronate EH, manufactured by Nippon Polyurethanes, NCO% = 21.3%)
While well stirring 150 parts of ethyl acetate and 100 parts of ethyl acetate at 80 ° C., 10 parts of polydimethylsiloxane (molecular weight: 2,200) having the structure of Reference Example 1 was gradually dropped therein and reacted. Then, while stirring well at 50 ° C., 7 parts of polydimethylsiloxane (molecular weight: 1,800) having amino groups at both ends having the above structure are gradually dropped, and 72 parts of γ-mercaptopropyltrimethoxysilane are gradually dropped. To give a reaction product (3).

The obtained reaction product (3), according to the infrared absorption spectrum, observed absorption by free isocyanate groups 2,270Cm ^-1, also, -S on 1,090Cm ^-1
The absorption band based on the iO-group was shown. Further, when the free isocyanate groups of the reaction product (3) were quantified, the theoretical value was 6.6%, whereas the measured value was 5.
7% (as pure). Finally, ethyl acetate was added to obtain a resin solution (C) of a reference example having a solid content of 50%.

Example 1 100 parts of the resin solution (A) of Reference Example 1, 300 parts of methyl ethyl ketone, 0.5 part of water and 0.01 part of tin octylate were blended and stirred well to give a resin compound solution of the present invention. Obtained. Example 2 100 parts of the resin solution (A) of Reference Example 1, 10 parts of a nitrocellulose resin (solid content: 20%, manufactured by Daicel Chemical Industries, Ltd.), 306 parts of methyl ethyl ketone, 0.5 part of water, and 0.01 part of tin octylate Was mixed and stirred well to obtain a resin compound solution of the present invention.

Example 3 100 parts of the resin solution (B) of Reference Example 2, 300 parts of methyl ethyl ketone, 0.5 part of water and 0.01 part of tin octylate were blended and stirred well to give a resin compound solution of the present invention. Obtained. Example 4 100 parts of the resin solution (B) of Reference Example 2, 10 parts of a silicone-polyurethane resin [solid content: 20%, manufactured by Dainichi Seika Kogyo Co., Ltd. (Dialomer)], methyl ethyl ketone 306
Parts, water 0.5 parts and tin octylate 0.01 parts,
By stirring well, a resin compound solution of the present invention was obtained.

Example 5 100 parts of the resin solution (C) of Reference Example 3, 300 parts of methyl ethyl ketone, 0.5 part of water and 0.01 part of tin octylate were mixed, and the mixture was thoroughly stirred to give a resin compound solution of the present invention. Obtained. Example 6 100 parts of the resin solution (C) of Reference Example 3 and polyvinyl butyral resin [solid content: 20%, manufactured by Sekisui Chemical Co., Ltd.] 1
0 parts, 306 parts of methyl ethyl ketone, 0.5 parts of water and 0.01 parts of tin octylate were mixed and stirred well to obtain a resin compound solution of the present invention.

Comparative Example 1 150 parts of polybutylene adipate (molecular weight: 2,000) and 15 parts of 1,3-butanediol were dissolved in 200 parts of methyl ethyl ketone and 50 parts of toluene. 6 parts in methyl ethyl ketone
A solution in which 2 parts of water-added MDI was dissolved was gradually added dropwise, and after completion of the addition, the mixture was reacted at 80 ° C. for 6 hours. This solution had a solid content of 35% and had a viscosity of 24,000 cps (20 ° C.). Further, 100 parts of the resin solution, silicone oil [SH-200, Toray Dow Corning Co., Ltd.]
A mixed solution consisting of 3 parts and 300 parts of methyl ethyl ketone was used as a resin compound solution for a comparative test.

Comparative Example 2 A resin mixture was prepared by mixing 100 parts of the same resin solution as in Comparative Example 1, 5 parts of Teflon powder (manufactured by Daikin Industries, Ltd.) and 345 parts of methyl ethyl ketone / toluene (= 1/1). An isocyanate (solid content: 75%, manufactured by Nippon Polyurethane Co., Ltd.) was added to the above compounded liquid with a resin liquid: isocyanate = 24
3 (weight ratio) were added to give a resin compound solution for a comparative test.

Evaluation as paint The resin compound solutions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were dried on one surface of a polyurethane belt for precision conveyance (manufactured by Nippon Siegling Co., Ltd.) to a thickness of 2 to 3 μm after drying. It was applied so that However, drying is natural drying (23 ° C,
(Humidity: 46%) and left for 3 days to measure various physical properties. Adhesion; cross-cut cellophane tape peeling test (cross cut method)
And evaluated. Static friction coefficient: The static friction coefficient of the film forming layer was evaluated by a surface property tester (manufactured by Shinto Kagaku). Abrasion resistance; Taber abrasion test (conditions: wear wheel CS-1)
Abrasion resistance test was performed (1,000 times) at 0, 1 kg of load and 70 rpm.

[0039]

[Table 1]

Evaluation when applied to magnetic recording material The resin compound solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were coated on a polyester film having a thickness of 11.5 μm.
Each was coated with a reverse roll coater so that the thickness after drying became 0.5 μm, to form a heat-resistant lubricating layer. Next, a magnetic layer is formed on the opposite surface from a dispersion of Co-containing γ-Fe ₂ O ₃ and a normal polyurethane resin and a vinyl chloride copolymer resin according to a conventional method, and cut into predetermined widths to form six magnetic layers each. Was obtained. The performance of these magnetic recording media was as shown in Table 2 below.

[0041]

[Table 2]

A: Coefficient of static friction of the lubricating layer B: Squeal of the tape when the tape is run 200 times as a video tape C: Lateral fluctuation of jitter as a video tape D: Fast forward as a video tape E: The state of abrasion of the lubricating layer after running 200 times as a video tape F: Comprehensive evaluation as a video tape

Evaluation as Releasable Coating Layer Each of the resin compound solutions of Examples 3 to 6 and Comparative Examples 1 and 2 was used, each having a 100% modulus of 60 kg / cm ² and a thickness of 50 kg.
The sample was uniformly coated on one side of a μm polyvinyl chloride film so that the thickness when dried was 0.1 μm, and the solvent was evaporated in a dryer to prepare a sample having a peelable film layer.
When the temperature was 100 ° C. or higher, the polyvinyl chloride film was softened, and the shape as the film could not be maintained. The samples were left at room temperature (23 ° C., humidity 46%) for 2 days and then subjected to each test. 20 m width on the coated base material thus produced
m of acrylic adhesive tape [manufactured by Sekisui Chemical Co., Ltd.] with a rubber roller of 2 kg in its own weight, at room temperature (23 ° C., humidity 46%) for one day and at high temperature (40 ° C., humidity 90% or more).
After 3 days respectively, the peeling force, residual adhesive force,
Remaining adhesive strength retention and peelability of the peelable film layer were measured for each item, and the results are shown in Table 3.

Peeling force : A pressure-sensitive adhesive tape having a width of 20 mm was attached to the peeling film layer, stored at 40 ° C. under a load of 20 g / cm ² for 24 hours, and then released at a speed of 300 mm / min.
The force (g) required for pulling and peeling at an angle of ° was measured (20 ° C.). Residual adhesive strength : The adhesive tape after the peelability measurement was adhered to a stainless steel plate # 280, reciprocated once over a 2 kg tape roller, and after 30 minutes, pulled at an angle of 180 ° at a speed of 300 mm / min and peeled. The force (g) required for the measurement was measured (20 ° C.). Residual adhesive strength retention rate : Percentage of residual adhesive strength when a clean adhesive tape not subjected to the above test was attached to a stainless steel plate # 280 and the adhesive strength (320 g / 20 mm) to the stainless steel plate was set to 100%. ing. Dropping property : A dropping test of the stripping film layer is performed on the sample after the gauze is reciprocated once under a load of 50 g / cm ^{2 on} the stripping film layer.

[0045]

[Table 3] A: One day after room temperature (23 ° C., humidity 46%) B: Three days after high temperature (40 ° C., humidity 90% or more) * 1: The peelable film layer was broken.

[0046]

As described above, since the polysiloxane resin compound of the present invention has at least one free isocyanate group and hydrolyzable silyl group, the resin is crosslinked by moisture or moisture in the air. One-part curing becomes possible,
The process of forming the coating layer can be simplified. In addition, the adhesion of the coating layer to the base sheet is improved by the presence of the free isocyanate. Further, the polysiloxane resin compound of the present invention can be applied to a paint, a binder for magnetic recording or thermal recording, a back coat agent, a release treatment agent, an overcoat agent, a hard coat agent and the like.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 175/04 C09D 175/04 183/04 183/04 // C09J 7/02 C09J 7/02 1-7-6, Nihonbashi Bakurocho, Chuo-ku, Tokyo Dainippon Seika Kogyo Co., Ltd. (72) Katsumi Kuriyama 1-7-6, Nihonbashi Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (56) References Special JP-A-6-313150 (JP, A) JP-A-7-157726 (JP, A) JP-A-55-98219 (JP, A) JP-A-2-2866757 (JP, A) JP-A-63-277222 (JP-A 63-277222) JP, A) JP-A-63-205116 (JP, A) JP-A-63-145321 (JP, A) JP-A-62-205116 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) C08G 77 / 445,18 / 61,18 / 70 C08L 83/04

Claims (1)

(57) [Claims] 1. A compound containing a resin having a siloxane segment, wherein the resin comprises a polysiloxane compound having a reactive organic functional group and a silane coupling agent having a reactive organic functional group other than an isocyanate group. A one-part curable polysiloxane resin compound, which is a reaction product with an organic polyisocyanate and comprises a resin having at least one free isocyanate group.