JP2005325242A - Coating composition and coating layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition capable of forming a high functional and non-tacky coating layer having both excellent non-tacky performance and other properties such as antistatic properties and hardness (durability), and a coating layer. <P>SOLUTION: This coating composition comprises a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer (e.g., an isocyanate curing agent), and a conductive material, and the conductive material accounts for ≤80%, by weight, to the weight sum of the fluorine-siloxane graft polymer and the conductive material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a paint composition and a coating layer formed thereby, and more particularly to a paint composition suitable for use as a paint requiring high non-tackiness and a coating layer thereof.

Conventionally, a fluororesin or a silicone resin is used for the base of the non-adhesive paint. Further, siloxane graft polymers such as urethane resins or acrylic resins obtained by graph polymerization of monomers having silicone groups are also used. Since this siloxane graft polymer has not only high non-adhesiveness but also heat resistance, it is used as a heat-resistant protective layer for metal thin film layers such as heat-sensitive recording media (Patent Document 1).
JP-A-6-255242

  However, fluororesins and silicone resins that are generally used when high non-adhesiveness is required are generally soft. In order to improve this point, if a hard filler component is added, non-adhesiveness decreases, which may not be preferable depending on the application. Further, a general siloxane graft polymer could not obtain a sufficiently high non-adhesive performance required for the application depending on the application.

  As described above, non-adhesiveness is required, and when a fluororesin or silicone resin alone is used, the coating layer is soft and easily damaged, and even if it exhibits high non-adhesiveness in the initial state, it is used. In some cases, the non-adhesiveness was significantly reduced. In addition, organic powders that are light in specific gravity and easily charged can adhere to the coating layer even if the coating layer is formed from a coating composition with anti-static properties. Couldn't get.

  As mentioned above, organic powder processing equipment such as wheat flour, chemical processing equipment, film production processing equipment for display screens, kitchen-related products, life-related equipment, etc., in addition to non-adhesiveness, antistatic properties, hardness A highly functional non-adhesive coating layer having other characteristics such as (durability) is strongly demanded.

  An object of the present invention is to provide a coating composition and a coating layer capable of forming a highly functional non-adhesive coating layer having excellent non-adhesive performance and other characteristics such as antistatic property and hardness (durability). It is to provide.

  The coating composition of the present invention is a coating composition comprising a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer, and a conductive material. In the coating composition, the weight ratio of the conductive material to the total weight of the fluorine-siloxane graft polymer and the conductive material is 80% or less.

  With this configuration, it is possible to form a hard coating layer having excellent hardness (durability), slipperiness, non-adhesiveness, and solvent resistance sufficient for practical use, and having a high degree of antistatic properties.

  Another coating composition of the present invention is a coating composition comprising a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer, and a ceramic and / or resin. In this coating composition, the weight ratio of the ceramics in the total weight of the fluorine-siloxane graft polymer and the ceramics is 80% or less, or the weight ratio of the resin in the total weight of the fluorine-siloxane graft polymer and the resin is 95% or less.

  With this configuration, it is possible to obtain a coating layer that is excellent in slipperiness, non-adhesiveness, and solvent resistance, and that is hard to be damaged by further improving the hardness (durability).

  Yet another coating composition of the present invention is a coating composition comprising a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer, a conductive material, and a ceramic and / or resin. The coating composition has a total weight ratio of 80% or less of the conductive material and ceramic in the total weight of the fluorine-siloxane graft polymer and the conductive material and ceramic, or the fluorine-siloxane graft polymer and the resin. The resin accounts for 95% or less by weight.

  With this configuration, in addition to non-adhesiveness, a coating layer having both excellent antistatic properties and high hardness (durability) can be formed. The above excellent antistatic property also effectively works to improve non-stickiness.

  Next, an embodiment of the present invention will be described. FIG. 1 is a diagram showing a state in which a coating composition 2 according to an embodiment of the present invention is applied to a wall 1 by, for example, spray coating and dried to form a coating layer 2. The coating composition comprises (a) a fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd., (b) a fluorine-siloxane graft polymer curing agent (for example, an isocyanate-based curing agent), and (c) a conductive material. (D) ceramics and (e) resin are shown. Among these, (a) a fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. and (b) a curing agent (for example, an isocyanate-based curing agent) of the fluorine-siloxane graft polymer are essential components. The conductive material, (d) ceramics, and (e) resin are selected compositions in which one or more of these are selected.

  Next, each composition among the coating compositions will be described. The coating composition having high non-adhesiveness according to the present invention has at least (a) a fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. and (b) a fluorine-siloxane graft polymer. A curing agent (for example, an isocyanate curing agent) and (c) a fibrous material coated with a conductive oxide are combined. (A) Fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. and (c) Fibrous material coated with conductive oxide occupies (c) conductive oxide. The weight ratio of the fibrous material is 80% or less. In this case, not only the antistatic property but also a sufficiently high hardness to withstand practical use can be obtained for the reason described later.

  When the antistatic property is considered to be hard, the coating composition includes (a) a fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd., and (b) a fluorine- A siloxane graft polymer curing agent (for example, an isocyanate curing agent) and (d) ceramics and / or (e) a resin, and (c) a conductive material (a fibrous material coated with a conductive oxide). May not be included. In this case, {(d) ceramics} / {(a) fluorine-siloxane graft polymer ZX series + (d) ceramics} manufactured by Fuji Kasei Kogyo Co., Ltd.] × 100% by weight ratio is 80% or less. Alternatively, {(e) resin} ÷ {(a) fluorine-siloxane graft polymer ZX series + (e) resin}] × 100% manufactured by Fuji Kasei Kogyo Co., Ltd. by weight ratio is set to 95% or less.

  In the case where both the antistatic property and the hardness are regarded as important in the coating composition, (a) a fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd., and (b) a fluorine- A siloxane graft polymer curing agent (for example, an isocyanate curing agent), (c) a fibrous material coated with a conductive oxide, and (d) ceramics and / or (e) a resin are combined. (A) Fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd., (c) Fibrous material coated with a conductive oxide, and (d) Ceramics occupying the total weight of the ceramic. The total weight ratio of the fibrous material coated with the conductive oxide and (d) ceramic is 80% or less, or (a) the fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. (E) The weight ratio of the resin to the total weight with the resin is 95% or less.

  Each component of the coating composition refers to a state before mixing, that is, a state prior to coating. The above components are cured by initiating a chemical reaction by mixing, for example, an isocyanate curing agent. The coating material in such a state is applied by various coating methods and dried to form a coating layer.

  The feature of the coating composition having high non-adhesiveness of the present invention is that it is made highly functional by adding an additive component using a fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. This makes it possible to realize a coating layer that is not soft and has a sufficiently high surface hardness, such as a fluororesin and a silicone resin, and on which high slipperiness and non-adhesiveness are formed. Therefore, even when a conductive material or a filler is included, a non-adhesive decrease is small, a powder non-adhesive property or a tape non-adhesive property is high, and a coating layer that is not easily damaged can be obtained.

  The above-mentioned fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. has a hydroxyl group, and a cured film (coating layer) is produced by polymerization with isocyanate or the like. Therefore, the ZX series raw material is preferable because it has a high surface hardness and provides a coating layer excellent in slipperiness, non-adhesiveness, and solvent resistance.

  In the embodiment of the present invention, (c) a conductive material (for example, a fibrous material coated with a conductive oxide) or (d) a ceramic (a) a fluorine-siloxane graft polymer manufactured by Fuji Kasei Kogyo Co., Ltd. The weight ratio with respect to the ZX series is in the range of 0 to 80% by weight. However, it is more preferably in the range of 10 to 50% by weight. That is, (c) conductive material and / or (d) occupying the total weight of (a) fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. and (c) conductive material and / or (d) ceramics The weight ratio of the ceramic is more preferably 10 to 50% by weight.

  (C) When the blending ratio of the conductive material is less than 5% by weight, the antistatic effect cannot be obtained, and when it exceeds 80% by weight, the smoothness and non-adhesiveness of the coating layer are lowered. When silicon carbide is used, surface hardness and wear resistance can be improved.

  In the embodiment of the present invention, (e) the blending ratio of the resin is (a) the fluorine-siloxane graft polymer ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. and (e) the total weight of the resin (e) the resin. The weight ratio is set to 0 to 95%. However, it is more preferably 30 to 90%. When a resin having a hardness such as an epoxy resin or a polyimide resin is selected as the resin, the surface hardness is further improved and scratch resistance and wear resistance are improved. In addition, the use of a resin having high chemical resistance such as an epoxy resin improves the solvent resistance. When the weight ratio of the resin exceeds 90%, the non-adhesiveness is drastically reduced. In the case of an epoxy resin, it can itself act as a curing agent for the fluorine-siloxane graft polymer ZX series of Fuji Kasei Kogyo Co., Ltd. Use of a fluororesin is effective in maintaining water repellency when worn.

  Examples of the fluorine-siloxane graft polymer ZX series of Fuji Kasei Kogyo Co., Ltd. used in the embodiment of the present invention include ZX-022H, ZX-007C, ZX-001, etc. good.

  Examples of the curing agent for the fluorine-siloxane graft polymer used in the embodiment of the present invention include an isocyanate curing agent and a blocked isocyanate. However, these are not particularly limited, and examples thereof include TPA-100, MF-B60X manufactured by Asahi Kasei Chemicals Corporation, and Cymel 325 manufactured by Mitsui Cyanamid Co., Ltd.

  An example of the liquid medium used in the embodiment of the present invention is an organic solvent. The organic solvent is not particularly limited, and examples thereof include toluene, xylene, methyl ethyl ketone, and Hisolv series manufactured by Toho Chemical Co., Ltd.

  The coating composition having high non-tackiness according to the embodiment of the present invention can be adjusted to a coating material by adding a coating compounding agent such as a pigment and a viscosity modifier dispersing agent to the coating composition. This paint is usually applied by spray coating, but can also be applied by brushing, impregnation, casting, or the like.

  This paint is excellent in non-adhesiveness and slipperiness and has a high surface hardness. Moreover, it has the same heat resistance, solvent resistance and chemical resistance as urethane resin. The surface hardness and chemical resistance can be improved by adding resin. Depending on the formulation of the paint, it can be cured at room temperature.

  Applications of the coating in the embodiment of the present invention can be used for coating hoppers and chutes of powder equipment, support rolls, films and adhesive tape-related rolls, food processing rolls, and the like.

  The chute and the hopper of the powder device covered with the coating layer in the embodiment of the present invention are excellent in non-adhesiveness, and are less likely to be contaminated by the adhesion of the powder, so that the labor of cleaning can be saved.

  The following examples further illustrate the present invention.

(Example 1)
Example 1 of the present invention is characterized in that it is a coating layer excellent in non-adhesiveness and antistatic properties. 20g of ZX series (ZX-022H: non-volatile content 45%), fluorine-siloxane graft polymer manufactured by Fuji Kasei Kogyo Co., Ltd., 10g of methyl ethyl ketone, isocyanate-based curing agent (Asahi Kasei) (Chemicals Co., Ltd.) 3.7g was stirred and mixed in the mixing tank. Next, 4 g of fibrous titanium oxide (Ishihara Sangyo Co., Ltd .: FT-3000) was added and mixed in the same manner to prepare a paint. Fibrous titanium oxide FT-3000 is coated with a conductive oxide. In this case, the conductive material blending ratio = [(conductive material weight) ÷ {(fluorine-siloxane graft polymer weight) + (conductive material weight)}] × 100% is 30% by weight. That is, the weight ratio of the conductive material to the total weight of the fluorine-siloxane graft polymer and the conductive material is 30%.

  This paint was applied on a stainless steel plate SUS304 and baked at 150 ° C. for 60 minutes to obtain a coating film having a thickness of 50 μm. This is the coating layer of Example 1 of the present invention. Further, as Comparative Example 1, a coating layer formed in the same manner as in Invention Example 1 except that fibrous titanium oxide was blended in the same manner as in Invention Example 1 was used when the coating layer of Invention Example 1 was prepared. In addition, an antistatic fluororesin coating NF-004EC manufactured by Nippon Fuso Kogyo Co., Ltd. was used as Comparative Example 2 for verification of the flour adhesion described below.

  Further, as a substitute for a fluorine-siloxane graft polymer manufactured by Fuji Kasei Kogyo Co., Ltd., a coating layer obtained by baking 20 μm of polysiloxane graft polymer (manufactured by Nippon Shokubai Co., Ltd .: SG-204) on SUS304 was used as Comparative Example 3.

The above-mentioned test body coating layer was subjected to measurement of leakage resistance value, pencil hardness test, and tape adhesion test. In the case of the antistatic coating layer, the leakage resistance value is preferably as low as possible. In the pencil hardness test, when the tip is scratched with a pointed pencil tip, for example, when it is torn with a 2H hardness core, the hardness of the coating layer is H. In the tape adhesion test, a 25 mm wide gum tape made by Nitto Tape Co., Ltd. was adhered and the load required for peeling was measured. The smaller the load value, the better the non-adhesiveness. In the flour adhesion test, non-adhesive superiority or inferiority is observed by appearance observation after each procedure. The wheat flour adhesion test was performed according to the following procedure.
(Procedure 1) Place flour on the panel and drop it by gravity.
(Procedure 2) The panel of Procedure 1 is carefully wiped with Kim Towel (manufactured by Crecia Co., Ltd.), and the flour is similarly placed on the panel and dropped by gravity.
(Procedure 3) Wash the panel of Procedure 2 with water, clean it with acetone, place the flour on the panel and drop it by gravity.

  Table 1 shows the results of the flour adhesion test on the above-mentioned coating layer specimen (Invention Example 1, Comparative Examples 1 to 3).

  From Table 1, Example 1 of the present invention is slightly superior to Comparative Example 1 in terms of tape adhesion, but is definitely superior to Comparative Example 3. In addition, it can be seen that the leakage resistance value is lower than those of Comparative Example 1 and Comparative Example 2, and is excellent in antistatic. In the pencil hardness test, hardness H was obtained for both Example 1 and Comparative Examples 1 and 3. This is sufficiently high hardness as an antistatic non-adhesive coating layer.

  The external appearance of the flour adhesion test is shown in FIGS. In Comparative Example 1, no adhesion of the flour was observed after the procedures 1 and 3, but a lot of flour was observed after the procedure 2. In Comparative Example 2, the adhesion of flour was observed after procedures 1, 2, and 3. On the other hand, no adhesion of the flour was observed in the coating layer of Example 1 of the present invention after any procedure 1-3. Therefore, for example, in the tape adhesion test, it seems that Comparative Example 1 is slightly superior in non-adhesiveness compared to the adhesion force <1 N of Comparative Example as compared to the adhesion force <1.2 N of Invention Example 1. FIG. In the flour adhesion test shown in (a) to FIG. 2 (c), it can be seen that Example 1 of the present invention is superior to Comparative Example 1 in terms of non-adhesion.

(Example 2)
Example 2 of the present invention is characterized in that it is a hard coating layer excellent in non-adhesiveness and having increased hardness of the coating layer. 20 g of ZX series (ZX-022H: non-volatile content 45%) of fluorine-siloxane graft polymer manufactured by Fuji Kasei Kogyo Co., Ltd. 7 g, 20 g of epoxy resin (Arakawa Industrial Chemical Co., Ltd .: E-102) and 1.5 g of phenol resin (Tamanol 759 manufactured by Arakawa Chemical Co., Ltd.) were stirred and mixed in a mixing tank. This paint was applied on SUS304 and baked at 220 ° C. for 60 minutes to obtain a coating layer having a thickness of 50 μm. This coating layer was referred to as Invention Example 2. A taper abrasion test was conducted to measure the amount of wear of the coating layer by applying a pencil hardness after 12 hours of acetone immersion in the initial phase of the coating layer and the adhesive strength of the tape and a rotating abrasion body to the coating layer of the specimen. It was. In the Taber abrasion test, a wear wheel CS-10 was used, a load of 500 gf was applied, and the amount of abrasion was measured after 1000 revolutions. The pencil hardness test after immersion in acetone is a test for investigating solvent resistance. For comparison, the same test was performed for Comparative Example 1 described above. The results are shown in Table 2.

  According to Table 2, the coating layer of Example 2 of the present invention is much superior to Comparative Example 1 in hardness, although it is slightly inferior to Comparative Example 1 in tape adhesion, regardless of whether it is initial or after acetone immersion. Reflecting this difference in hardness, in the Taber abrasion test, the wear amount of the coating layer of Example 2 of the present invention is reduced to about 1/10 of that of Comparative Example 1. The results of this test indicate that the tape non-adhesiveness is maintained while it has sufficient hardness and softening by the solvent is suppressed, and has sufficient performance. In addition, a significant improvement in wear resistance was confirmed.

  Next, although it may be contained in the said embodiment of this invention, the modification of embodiment of this invention is given and enumerated.

  The conductive material may be any of a fibrous titanium oxide coated with a conductive oxide and a conductive inorganic material filler.

  With this configuration, antistatic properties can be obtained using a material having durability in the coating layer. At the same time, the rigidity can be improved.

  The conductive oxide may be tin oxide and / or antimony oxide.

  According to this configuration, the antistatic property can be further improved by including the conductive material in the coating layer by the coating coating material that is easy to manufacture.

  The ceramics may be fibrous silicon carbide and / or granular silicon carbide.

  With this configuration, it is possible to easily disperse uniformly in the coating layer and to combine both hardness and non-adhesiveness.

  The resin may be any of an epoxy resin alone, an epoxy resin and a phenol resin that is a curing agent thereof, and a fluororesin.

  This configuration also makes it possible to obtain hardness as well as non-adhesiveness.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is limited to these embodiments. There is no. The scope of the present invention is indicated by the description of the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope.

  According to the coating composition and the coating layer of the present invention, the non-adhesiveness and the hardness or the antistatic property which cannot be realized in the fluororesin and general polysiloxane graft polymer are secured, and these characteristics are deteriorated by the solvent. Is small. For this reason, it is expected to be widely used for coating layers of processing apparatuses such as chemicals, powders, foodstuffs, semiconductor devices, and liquid crystal display devices.

It is a figure which shows the state which used the coating composition in the embodiment of this invention, and formed the coating layer by spray-coating the coating composition. It is a figure which shows the flour adhesion test in Example 1, (a) is a figure after the procedure 1, (b) is after the procedure 2, and (c) is a figure which shows the state after the procedure 3.

Explanation of symbols

  1 wall, 2 coating layer.

Claims (9)

A coating composition comprising a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer, and a conductive material,
The coating composition wherein the weight ratio of the conductive material to the total weight of the fluorine-siloxane graft polymer and the conductive material is 80% or less. A coating composition comprising a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer, and ceramics and / or resin,
The weight ratio of the ceramic in the total weight of the fluorine-siloxane graft polymer and the ceramic is 80% or less, or the weight ratio of the resin in the total weight of the fluorine-siloxane graft polymer and the resin is 95. %, A coating composition. A coating composition comprising a fluorine-siloxane graft polymer, a curing agent for the fluorine-siloxane graft polymer, a conductive material, and ceramics and / or resin,
The weight ratio of the sum of the conductive material and the ceramic in the total weight of the fluorine-siloxane graft polymer and the conductive material and the ceramic is 80% or less, or the fluorine-siloxane graft polymer, The coating composition whose weight ratio of the said resin to the weight sum with resin is 95% or less.   The coating composition according to claim 1 or 3, wherein the conductive material is any one of fibrous titanium oxide coated with a conductive oxide and a conductive inorganic material filler.   The coating composition according to claim 4, wherein the conductive oxide is tin oxide and / or antimony oxide.   The coating composition according to any one of claims 2 to 5, wherein the ceramic is fibrous silicon carbide and / or granular silicon carbide.   The coating composition according to any one of claims 2 to 6, wherein the resin is one of an epoxy resin alone, an epoxy resin and a phenol resin that is a curing agent thereof, and a fluororesin.   The coating composition according to any one of claims 1 to 7, wherein the fluorine-siloxane graft polymer is any one of the fluorine-siloxane graft polymers ZX series manufactured by Fuji Chemical Industry Co., Ltd.   A coating layer formed by applying the paint composition according to claim 1 as a paint.