JP2002322432A - Non-sticky abrasion-resistant coating composition and non-sticky abrasion-resistant coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-sticky abrasion resistant coating fluorine resin composition excellent in heat resistance, a releasing property (a non-sticky property) and endurance (an abrasion resistance) and also capable of maintaining the excellent releasing property for a long time, and a coated article having a coated film from the coating material composition. SOLUTION: This non-sticky, abrasion-resistant coating material consists of an aqueous dispersion of the melt-processable perfluoro copolymer particles, an organic filler and an inorganic filler, in which <100 pts.wt. organic filler and 5-60 pt.wt. inorganic filler based on 100 pt.wt. solid portion of the melt- processable perfluoro copolymer particles are contained, and the coated article is obtained by coating the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fluororesin paint characterized by non-adhesiveness, and particularly to a paint composition excellent in non-adhesiveness and abrasion resistance, and a metal composition comprising the same. The present invention relates to a coated article coated on a substrate.

[0002]

2. Description of the Related Art Fluororesins have the lowest surface energy as compared with other general-purpose plastics, and generally have the property that substances are difficult to adhere to. Therefore, utilizing this property, the fluororesin coating is used in various fields where non-adhesion is required.

[0003] As an example of its use, there is a home appliance / kitchen application. That is, it is a kitchen appliance such as a frying pan or a pan, and a household electric appliance such as a rice cooker or a hot plate. It is also used inside microwave ovens and inside jar pots.

[0004] In recent years, applications in the OA field, in which technological progress has been remarkable, have been actively performed. As an example, there is a coating on the surface of a fixing roll, which is a fixing component of a copier, a laser beam printer, a facsimile, and the like. It is also applied to coating the surface of a separation claw that separates and guides copy paper from a roll.

For example, in the case of a fixing roll, it is necessary to heat and melt the toner on the surface of the fixing roll to fix the toner on the paper surface, but it is necessary to avoid adhesion of the toner to the roll itself. If toner adheres to the roll surface, it may cause offset or stain on the back of the paper. Therefore, the above-mentioned characteristics are improved by providing a fluororesin layer having excellent release properties and excellent heat resistance on the surface of the fixing roll.

As the fluororesin used in these applications, polytetrafluoroethylene (PTF), which is a homopolymer of tetrafluoroethylene (TFE), has been used.
E) has been frequently used. Although PTFE is excellent in release property (non-adhesiveness) and heat resistance, it cannot be melt-processed, so it is unavoidable that fine voids exist on the surface of the obtained coating film. There is a disadvantage that the toner enters the toner and the releasability gradually decreases.

In recent years, a copolymer of TFE and perfluoro (alkyl vinyl ether) (PFA) has been used in place of PTFE for the purpose of improving the releasability and durability. PFA has the same heat resistance as PTFE,
In addition, since PTFE can be melt-processed, there are no voids in PTFE that can be obtained, and the mold releasability at the initial stage and over time is excellent.

[0008] On the other hand, PFA is excellent in the above properties, but has low abrasion resistance. When used for a long period of time, the PFA layer is worn away, and the primer and the substrate may be finally exposed. Therefore, there is a need for a fluororesin coating composition that has improved durability, that is, abrasion resistance, while maintaining excellent heat resistance and workability of PFA.

[0009]

SUMMARY OF THE INVENTION Generally, PFA and TFE
-Hexafluoropropylene (HFP) copolymer (FE
Melt-processable perfluoro-based copolymers such as P)
Although it has a very good performance in terms of releasability and non-adhesion, the coating film strength is particularly reduced when heated. Therefore, the durability is lower than that of PTFE. Heretofore, the approach of improving the fluororesin itself has been carried out in order to improve this disadvantage. However, it is difficult to greatly improve the durability of the melt-processable fluororesin by changing the monomer composition, molecular weight, and the like, in order to maintain excellent properties comparable to PTFE. On the other hand, in PTFE, obtaining a pinhole-less coating film such as a perfluoro-based copolymer that can be melt-processed while maintaining its release property and durability is difficult to obtain by using PTFE.
It is technically very difficult in view of the essential property that E cannot be melt-processed.

Therefore, the inventors of the present invention have a releasability (non-adhesiveness).
For the purpose of imparting durability to a melt-processable perfluoro-based copolymer having excellent non-adhesiveness, it was studied to add PTFE as an organic filler instead of a base polymer.

However, simply adding PTFE as an organic filler to a melt-processable perfluoro-based copolymer such as PFA or FEP not only makes it impossible to make use of both properties, but also conversely releases moldability (non-removable). (Adhesiveness) and durability cannot be satisfied.

In view of the problems and studies described above, the present inventors have further studied the fluororesin-based coating composition, and have obtained a melt-processable coating having excellent heat resistance and release properties (non-adhesiveness). A perfluoro-based fluororesin that can be melt-processed by blending a perfluoro-based fluororesin with an organic filler with excellent abrasion resistance and releasability and an inorganic filler for reinforcement at a specific ratio Mold release and heat resistance,
It has been found that durability can be imparted without impairing workability.

An object of the present invention is to provide a fluororesin based resin which is excellent in heat resistance, releasability (non-adhesiveness) and durability (abrasion resistance) and can maintain excellent releasability even after long-term use. And a coated article having a coating film of the coating composition.

[0014]

That is, the present invention comprises an aqueous dispersion of perfluoro-type copolymer particles which can be melt-processed, an organic filler and an inorganic filler. The present invention relates to a non-adhesive abrasion-resistant coating composition containing less than 100 parts of an organic filler and 5 to 60 parts of an inorganic filler based on 100 parts by weight of a solid content of polymer particles (hereinafter referred to as “parts”). .

As the melt-processable perfluoro-based copolymer, a copolymer of TFE with perfluoro (alkyl vinyl ether) and / or perfluoro (alkyl vinyl) is preferably used.

The organic filler has a number average molecular weight of 5
Particles of PTFE of more than 100,000 are preferred.
More preferably, the particles are incorporated in the form of an aqueous dispersion.

The inorganic filler includes potassium titanate whiskers having an average fiber length of 1 to 200 μm, titanium oxide whiskers having an average fiber length of 1 to 200 μm, zinc oxide whiskers having an average fiber length of 1 to 200 μm, and an average particle diameter of 0 to 200 μm. Aluminum oxide powder having an average particle diameter of 0.1 to 30 μm, zirconium oxide powder having an average particle diameter of 0.1 to 30 μm, and / or silicon oxide powder having an average particle diameter of 0.1 to 30 μm are preferred.

The non-adhesive wear-resistant paint composition is applied on a metal substrate via a primer layer composed of a fluororesin and a heat-resistant resin or a primer layer composed of a fluororesin, a heat-resistant resin and an aluminum oxide powder, and fired. By doing so, it is possible to provide a non-adhesive wear-resistant coated article in which a fired layer of the non-adhesive wear-resistant coating composition is formed on the primer layer.

From another viewpoint, the present invention relates to a non-adhesive abrasion-resistant paint composition comprising an aqueous dispersion of melt-processable perfluoro-based copolymer particles, an organic filler and an inorganic filler. In addition, when a coated article having a fired layer of the non-adhesive abrasion-resistant coating composition as a top coat layer was measured under the following conditions (hereinafter, referred to as "specific conditions"), a hot Taber abrasion test and a thrust abrasion test were performed. A non-top coat non-abrasive material having a wear amount of less than 1 mg and a coated article having a contact angle with hexadecane of 40 ° or more on the surface of each coated article after the hot Taber abrasion test and the thrust abrasion test, respectively. The present invention relates to an adhesive and abrasion-resistant coating composition.

[0020] Symbol pure aluminum plate was roughened surface roughness Ra3μm by test coated article sandblasting, via a primer layer having a thickness of 10 to 15 [mu] m, the thickness 20~25μ as a top coat layer
m, a coated article having a fired layer of a non-stick, abrasion-resistant coating composition.

Hot Taber Abrasion Test Using a heating type Taber abrasion tester, a wear wheel having an electronic copying paper fixed on its surface is heated to 200 ° C. and rotated at 60 rpm.
m, with a load of 1 kg against the surface of the test painted article,
The process is performed until the top coat layer is worn and the primer layer is exposed. The evaluation is based on the weight of the test painted article every 1000 revolutions, based on the weight of the test painted article after the first 100 revolutions, and averages the weight loss (mg) every 1000 revolutions.

Thrust Abrasion Test Using a friction abrasion tester, a stainless steel abrasion wheel is rotated at a load of 700 g and a linear velocity of 200 mm / sec, and pressed against the coated article for 1 hour. The evaluation is made based on the weight loss (mg) of the test painted article at the end of the test.

Hexadecane contact angle with hexadecane Using a surface contact angle meter, the hexadecane contact angle of each surface of the test coated article after the Taber abrasion test and the test coated article after the thrust abrasion test was measured at five points. ,
The average value is evaluated.

As the non-adhesive abrasion-resistant coating composition, the above-mentioned coating composition is preferable.

The present invention further provides, as a top coat layer, a fired layer of a non-adhesive abrasion-resistant coating composition comprising an aqueous dispersion of melt-processable perfluoro copolymer particles, an organic filler and an inorganic filler. A coated article having a wear amount of less than 1 mg in a hot Taber abrasion test and a thrust abrasion test when measured under the above specific conditions, and after the hot Taber abrasion test and the thrust abrasion test, respectively. The present invention relates to a non-adhesive abrasion-resistant coated article having a contact angle with hexadecane of 40 ° or more on the surface of the coated article.

In the non-adhesive wear-resistant coated article of the present invention,
As the non-adhesive abrasion-resistant paint composition, the above-mentioned non-adhesive abrasion-resistant paint composition is preferable, and the top coat layer is formed on a metal substrate, with a primer layer or a fluororesin made of a fluororesin and a heat-resistant resin. It is preferably formed via a primer layer composed of a heat-resistant resin and aluminum oxide powder.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The melt-processable perfluoro copolymer in the present invention includes a copolymer of TFE and perfluoro (alkyl vinyl ether) (PFA) or T
A copolymer of FE and perfluoro (alkyl vinyl) is preferably used. Examples of the perfluoro (alkyl vinyl ether) include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether) and the like, and particularly preferred is perfluoro (propyl vinyl ether). As the perfluoro (alkyl vinyl), hexafluoropropylene (HFP) is preferable. The copolymer of TFE and HFP (FEP) has heat resistance slightly inferior to PFA, but is excellent in mold releasability and processability like PFA. Although PFA and FEP are used in the examples of the present invention, the effects of the present invention are not limited to these perfluoro-based copolymers.

Since this perfluoro copolymer can be melt-processed, it is possible to form a fired layer without pinholes by firing after coating. Does not occur.

The melt-processable perfluoro copolymer is used in the form of an aqueous dispersion of the copolymer particles. This is because it is advantageous in that the preparation of the paint is easy and the production cost can be reduced. The average particle diameter of the copolymer particles is 0.05 to 0.7 μm, particularly 0.1 to
0.5 μm is preferred. The concentration of the aqueous dispersion is not particularly limited, and can be adjusted in a wide range of 20 to 80% by weight.

As the organic filler to be blended with the melt-processable perfluoro copolymer, PTFE particles are preferable, but any other organic filler having excellent wear resistance and releasability can be used. .

As the PTFE particles as the organic filler, high molecular weight PTFE particles are desirable. For example, in the case of PTFE having a number average molecular weight of less than 5,000,000, the durability of the PTFE particle itself is low, and even if it is blended with a perfluoro-based copolymer which can be melt-processed, the effect of improving abrasion resistance cannot be expected to be large.

When the PTFE particles are compounded as an organic filler, the PTFE particles can be mixed with an aqueous dispersion of a perfluoro copolymer which can be melt-processed in the form of an aqueous dispersion of PTFE, so that uniform mixing and dispersion can be achieved. Preferred from the point. PTF
The average particle diameter of the E particles is 0.05 to 0.7 μm, particularly 0.1 μm.
1 to 0.5 μm is preferred. The concentration of the PTFE aqueous dispersion is not particularly limited, and can be adjusted in a wide range from 20 to 80% by weight.

In the present invention, the amount of the organic filler to be added to the melt-processable perfluoro-based copolymer is limited to a specific range in order to secure and maintain non-adhesion and abrasion resistance. . That is, the solid content of the organic filler is less than 100 parts, preferably 20 to 9 parts, based on 100 parts of the solid content of the copolymer of the aqueous dispersion of the perfluoro copolymer which can be melt-processed.
9 parts, more preferably 25 to 65 parts. When organic fillers, especially high molecular weight PTFE particles, are added in this specific range, while maintaining the advantage of excellent non-stickiness of the perfluoro copolymer which can be melt-processed,
Abrasion resistance can be improved. If the amount of the organic filler is small, the effect of sufficiently improving the abrasion resistance cannot be obtained. Conversely, when the amount is large, the excellent processability and mold release effect of the perfluoro-based copolymer that can be melt-processed are not exhibited.

In the present invention, the inorganic filler is further blended in a specific ratio with the perfluoro copolymer which can be melt-processed. By blending the inorganic filler in a specific amount, the mechanical strength (durability) can be further improved without impairing the non-adhesive and abrasion resistance characteristics of the coating composition before the addition. The mixing ratio is 5 to 60 parts, preferably 8 to 40 parts, more preferably 8 to 40 parts, in terms of the solid content of the inorganic filler, with respect to 100 parts of the solid content of the copolymer of the aqueous dispersion of the perfluoro copolymer which can be melt-processed. Is 10 to 30 parts. By blending at this ratio, it is possible to further increase the mechanical strength of the coating film without developing adverse effects due to the blending of the inorganic filler. When the amount of the inorganic filler is small, a sufficient reinforcing effect cannot be obtained. Also,
When the amount is large, the characteristics inherent to the inorganic filler begin to appear on the coating film surface, and the decrease in non-adhesiveness becomes remarkable.

As the inorganic filler, a known inorganic filler can be used, but the reinforcing effect can be further enhanced by using an inorganic material having a particularly high hardness. Examples of the inorganic filler include inorganic whiskers having an average fiber length of 1 to 200 μm, preferably 10 to 100 μm, and inorganic powders having an average particle diameter of 0.1 to 30 μm, preferably 0.5 to 5 μm. Specific examples include inorganic powders such as potassium titanate whiskers, titanium oxide whiskers, inorganic whiskers such as zinc oxide whiskers, aluminum oxide powder, zirconium oxide powder, and silicon dioxide powder, but are not limited thereto. . Also,
It is also possible to use two or more kinds in combination. Further, if necessary, it is also possible to use an inorganic filler surface-treated by a known method, and by performing an appropriate surface treatment, dispersibility is further improved or affinity is improved. , Can be expected to enhance the reinforcing effect.

The coating composition of the present invention may contain various additives usually added to the coating composition, such as a surfactant and a coloring agent.

As the surfactant, various fluorine-containing surfactants can be used, and in the case of a non-fluorine surfactant, a nonionic surfactant is preferable. The addition amount is preferably 10 parts or less, particularly preferably 0.1 to 10 parts, per 100 parts of the solid content of the copolymer of the aqueous dispersion of the perfluoro copolymer which can be melt-processed. If the amount of the surfactant is too small, the effect of improving the dispersibility of the desired copolymer particles cannot be obtained.If the amount is too large, the ability of the copolymer particles to form a coating film is impaired and the non-adhesiveness is reduced. is there.

Examples of the coloring agent include, for example, inorganic pigments such as carbon black and composite oxide pigments (however, excluding the inorganic filler used in the present invention).
It is not limited to these. From the viewpoint that the non-adhesiveness of the formed coating film is not reduced, the addition amount is set to 100 parts or less based on 100 parts of the copolymer solid content of the aqueous dispersion of the melt-processable perfluoro copolymer. Is desirable.

The method for preparing the non-adhesive abrasion-resistant coating composition of the present invention is not particularly limited. For example, a melt-processable aqueous dispersion of a perfluoro copolymer is placed in a mixer such as a propeller-type stirrer, and the organic dispersion is added thereto. A method in which a predetermined amount of the aqueous dispersion of the filler and the inorganic filler in a dry state are mixed and uniformly mixed with stirring can be adopted. When PTFE particles are used as the organic filler, the PTFE particles are liable to become fibers by stirring, so care must be taken not to apply excessive shearing force.

The coating composition of the present invention thus obtained is
Although it depends on the coating method, the solid content is usually 10-60.
It is adjusted to the range of weight%.

The non-adhesive abrasion-resistant coating composition of the present invention can be applied to an object to be coated composed of various inorganic bases such as a metal base such as aluminum, iron and stainless steel and a ceramic base such as glass and porcelain. By firing at a temperature in the range of 200 to 400 ° C. after coating, a fired layer having excellent non-adhesiveness, abrasion resistance, and mechanical strength is formed. The coating film thickness may be appropriately selected depending on the application and the application portion, but from the viewpoint of corrosion resistance and the like, the film thickness after firing is 1
It is preferable to apply the coating so as to have a thickness of 0 μm or more, preferably 15 μm or more.

The coating composition of the present invention can be applied alone to a substrate to be coated, but may have low adhesion to the substrate. In such a case, coating with a primer for a fluororesin greatly improves the adhesion to the substrate. The thickness of the primer layer after firing is usually about 10 to 15 μm.

As such a primer coating, a conventionally known primer coating for a fluororesin coating composition can be used according to the type of the substrate. For example, for a metal substrate, a primer coating composed of a fluororesin and a heat-resistant resin, or a primer coating composed of a fluororesin and a heat-resistant resin and aluminum oxide powder, It is preferable from the viewpoint of good adhesion.

Examples of the fluororesin for the primer include polytetrafluoroethylene (PTFE), FE
P, PFA and the like, and examples of the heat-resistant resin include polyamide imide (PAI) and polyether sulfone (P
ES) and the like, but are not limited thereto.

The present invention also relates to the coated article thus obtained, in particular to a coated article having a fired layer of a non-adhesive wear-resistant coating composition formed on a metal substrate via a primer layer.

The coated articles of the present invention are useful for kitchen-related articles, home-appliance-related articles, OA-related articles, and industrial articles which conventionally use a melt-processable fluororesin.
Further, since PTFE which cannot be melt-processed conventionally is used, it can be used particularly for applications requiring durability and abrasion resistance.

More specifically, the following coated articles can be mentioned.

Kitchen-related articles: range cooker, frying pan, pan, etc.

Home appliance related articles: hot plate, rice cooker,
Inside of the jar pot

OA-related articles: fixing rolls of printers and electrostatic copying machines, separation claws of printers and electrostatic copying machines, etc.

In the course of studying the scope of application, the present inventors have found that the application of the fluororesin coating film, particularly to the rolls of OA-related equipment, particularly the fixing roll, has an effect that is correlated with the evaluation results of the actual machine. Characteristic was found.

In other words, the evaluation of the characteristics of the actual machine includes the prevention of adhesion of the toner to the roll (non-adhesiveness and releasability), the degree of wear by the paper edge and the paper separating claw (abrasion resistance and durability).
Is an important item, the evaluation of non-adhesion has a good correlation with the contact angle of hexadecane on the roll surface, and the evaluation of durability (abrasion resistance) is based on the evaluation The results of the abrasion test and the thrust abrasion test have a good correlation with the results of abrasion by the paper edge and the separating claw, respectively.

Based on these new findings, a non-adhesive abrasion-resistant paint composition which gives appropriate fixing roll characteristics was examined. The contact angle with hexadecane measured under the above specific conditions was 40 ° or more, It has been found that a coating composition that gives a coated article having an abrasion amount of less than 1 mg in the abrasion test and the thrust abrasion test has excellent roll characteristics in an actual machine.

Accordingly, the present invention also provides a non-adhesive abrasion-resistant paint composition comprising an aqueous dispersion of perfluoro-based copolymer particles which can be melt-processed, an organic filler and an inorganic filler. When a coated article having a fired layer of the abrasion-resistant coating composition as a top coat layer is measured under the above-mentioned specific conditions, the amount of wear in the Taber abrasion test and the thrust abrasion test under heat is less than 1 mg, and The present invention relates to a coated article having a contact angle with hexadecane of 40 ° or more on the surface of each coated article after a Taber abrasion test and a thrust abrasion test, and a non-adhesive abrasion-resistant coating composition for a top coat capable of providing the coated article.

When the contact angle with respect to hexadecane is 40 degrees or more, the non-adhesiveness to the toner of the copying machine is good.
When the temperature is lower than 40 degrees, the non-adhesiveness is low and the releasability of the toner is reduced.

The results of the hot Taber abrasion test relate to the abrasion of the paper edge. If the amount of abrasion under the specific conditions is less than 1 mg, the abrasion resistance is good. Similarly, if the amount of abrasion in the thrust abrasion test is less than 1 mg, it can be said that the abrasion of the separation claw is good.

With respect to the aqueous dispersion of perfluoro-based copolymer particles which can be melt-processed, the organic filler and the inorganic filler constituting the non-adhesive wear-resistant coating composition, the above description and specific examples can be applied.

Further, as the coated article, an article in which a fired layer of a non-adhesive wear-resistant paint composition is provided as a top coat layer on a metal substrate via the above-mentioned primer layer is preferable.

According to these evaluation methods, it is possible to evaluate coating film performance without conducting an actual machine test, so that the time required for material development can be greatly reduced.

[0061]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. In Examples and Comparative Examples,
All “parts” represent “parts by weight”, and all “%” represent “% by weight”. The drying and firing conditions are all conditions at the actual temperature.

Examples 1 to 3 and Comparative Examples 1 to 4 (Preparation of coating composition) Particles of PFA (TFE / perfluoro (propyl vinyl ether) = 95/5 mol%) (average particle diameter: 0.2 μm) Aqueous dispersion (concentration 65
%) And PTFE (number average molecular weight 50) as an organic filler.
Table 1 shows an aqueous dispersion of particles (average particle diameter: 0.3 µm) and potassium titanate whisker (Dentol WK200B manufactured by Otsuka Chemical Co., Ltd., fiber length: 10 to 20 µm) as an inorganic filler. The mixture was stirred for 15 minutes with a propeller-type stirrer at a ratio (solid content) shown in Table 1 to prepare a coating composition.

(Preparation Procedure of Test Coated Plate) A coated plate used for evaluating the performance of a coating film was prepared in the following procedure. (1) Substrate: pure aluminum plate (size is predetermined for each test) (2) Roughening: sand blast (Ra = 3 μm) (3) Primer coating: Primer coating by air spray on the substrate EK-1908 manufactured by Daikin Industries, Ltd.
GY) is applied to a thickness of 10 to 15 μm. Immediately after coating, drying is performed at 90 ° C. for 10 minutes, followed by cooling after drying. (4) Topcoat coating: A coating compounded as an example and a comparative example was coated with an air spray to a film thickness of 20 to 25 μm.
Paint with m. After drying at 90 ° C for 10 minutes, 15 minutes at 380 ° C
After baking for minutes, the sample was air-cooled to obtain a test coated plate.

The following tests were performed on the prepared test coated plates. Table 1 shows the results.

(Test Method) (1) Hot Taber Abrasion Test Using a heated type Taber abrasion tester (special type No. 101) manufactured by Yasuda Seiki Seisakusho, load 1 kg, double-sided adhesion to aluminum wear wheel A commercially available PPC paper is adhered with a tape to form a worn wheel.

After fixing the test coated plate to the apparatus, the surface temperature was 200
Check that the temperature has reached ℃ and start the test. First 10
Zero rotation is performed as a break-in operation. Thereafter, the sample is removed, the weight of the coated plate is measured, and the test coated plate is set in the apparatus again to start the test. After the 1000 rotation operation, the test coated plate is removed and the weight is measured. This is repeated up to 10 times until the top coat layer is worn and the primer layer is exposed.

From the above test, the average value of the weight loss (mg) every 1000 rotations is determined.

(2) Thrust wear test A friction wear tester (EFM-II) manufactured by Orientec Co., Ltd.
I-F), load 700 g, rotation 200 mm / s
At a linear speed of ec, the mating material is directly pressed against a stainless steel wear wheel. The test time is one hour, and the weight loss (mg) before and after the test is calculated. Regarding the results of this thrust abrasion test, not only the above-described testing machine but also a Suzuki Matsubara type abrasion testing machine having a similar friction and abrasion test method can provide equivalent test results.

(3) Measurement of Contact Angle with Hexadecane For each of the test coated plates after the tests of (1) and (2) above, the surface on which the abrasion test was not performed (untested surface) and the surface whose surface was abraded by the test The measurement of the contact angle with hexadecane on both sides (test surface) is performed by a surface contact angle meter (CA-A) manufactured by Kyowa Interface Science Co., Ltd. The measurement is performed at five points, and the average value is obtained.

[0070]

[Table 1]

Examples 4 to 6 and Comparative Examples 5 to 8 FEP was used as a melt-processable perfluoro copolymer.
Using an aqueous dispersion (concentration: 50%) of particles (average particle diameter: 0.2 μm) of (TFE / HFP = 85/15 mol%), the PTFE particles and the inorganic filler were mixed at the ratio shown in Table 2 (solid content). ) Was prepared in the same manner as in Example 1 to prepare a coating composition and a test-coated plate, and these test-coated plates were subjected to a hot Taber abrasion test, a thrust abrasion test, and hexadecane test in the same manner as in Example 1. Contact angle measurements were made. Table 2 shows the results.

[0072]

[Table 2]

[0073]

According to the present invention, fluorine which is excellent in heat resistance, releasability (non-adhesiveness) and durability (abrasion resistance) and can maintain excellent releasability even after long-term use. A resin-based non-adhesive wear-resistant coating composition and a coated article having a coating film of the coating composition can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Nobuyuki Tomibashi 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Koichiro Ogita 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin F-term (reference) in Yodogawa Seisakusho Co., Ltd. 4J038 CD121 CD122 CE051 GA12 HA216 HA246 HA446 KA08 KA19 MA02 MA08 MA10 NA05 NA11 PA19 PB02 PB09 PC02

Claims (12)

[Claims] 1. A melt-processable aqueous dispersion of perfluoro-type copolymer particles, comprising an organic filler and an inorganic filler, wherein the solid content of the melt-processable perfluoro-type copolymer particles is 100 parts by weight. A non-adhesive abrasion-resistant coating composition containing less than 100 parts by weight of an organic filler and 5 to 60 parts by weight of an inorganic filler. 2. The non-fluoropolymer according to claim 1, wherein the melt-processable perfluoro-based copolymer is a copolymer of tetrafluoroethylene with perfluoro (alkyl vinyl ether) and / or perfluoro (alkyl vinyl). Adhesive and abrasion resistant paint composition. 3. The organic filler according to claim 1, wherein the organic filler has a number average molecular weight of 5
3. A non-stick, abrasion-resistant coating composition according to claim 1 or 2, which comprises at least one million particles of polytetrafluoroethylene in the form of an aqueous dispersion. 4. The method according to claim 1, wherein the inorganic filler has an average fiber length of 1 to 20.
0 μm potassium titanate whiskers, average fiber length 1 to 1
200 μm titanium oxide whiskers, average fiber length 1-2
00 μm zinc oxide whiskers, average particle size 0.1-3
0 μm aluminum oxide powder, average particle size 0.1 to 3
A zirconium oxide powder having a particle diameter of 0 μm and / or a silicon oxide powder having an average particle diameter of 0.1 to 30 μm.
3. The non-adhesive abrasion-resistant coating composition according to any one of 3. 5. A non-adhesion resistant film having a fired layer of the non-adhesive wear-resistant paint composition according to claim 1 on a metal substrate via a primer layer comprising a fluororesin and a heat-resistant resin. Wear-painted articles. 6. A coating film of the non-adhesive wear-resistant coating composition according to claim 1, wherein a primer layer comprising a fluororesin, a heat-resistant resin and aluminum oxide powder is provided on a metal substrate. Non-adhesive wear-resistant painted article having 7. A non-stick, abrasion-resistant coating composition comprising an aqueous dispersion of melt-processable perfluoro copolymer particles, an organic filler and an inorganic filler, wherein the non-adhesive, abrasion-resistant coating composition is provided. When the coated article having the fired layer of the product as a top coat layer is measured under the following conditions, the amount of wear in the hot Taber abrasion test and the thrust abrasion test is less than 1 mg, and the hot Taber abrasion test and the thrust A non-adhesive abrasion-resistant coating composition for a top coat capable of providing a coated article having a contact angle with hexadecane of 40 ° or more on the surface of each coated article after the abrasion test. Serial to pure aluminum plate was roughened surface roughness Ra3μm by test coated article sandblasting, via a primer layer having a thickness of 10 to 15 [mu] m, the thickness 20~25μ as a top coat layer
m, a coated article having a fired layer of a non-stick, abrasion-resistant coating composition. Hot Taber Abrasion Test Using a heated Taber abrasion tester, heat the abrasion wheel with the electronic copy paper fixed on its surface to 200 ° C. and rotate at 60 rpm.
m, with a load of 1 kg against the surface of the test painted article,
The process is performed until the top coat layer is worn and the primer layer is exposed. The evaluation is based on the weight of the test painted article every 1000 revolutions, based on the weight of the test painted article after the first 100 revolutions, and averages the weight loss (mg) every 1000 revolutions. Thrust Abrasion Test Using a friction abrasion tester, a stainless steel abrasion wheel is rotated at a load of 700 g and a linear velocity of 200 mm / sec, and pressed against the coated article for 1 hour. The evaluation is made based on the weight loss (mg) of the test painted article at the end of the test. Using hexadecane contact angle surface contact angle meter, the hexadecane contact angle of each surface of the test coated article after the Taber abrasion test and each test coated article after the thrust abrasion test was measured at five points,
The average value is evaluated. 8. The non-stick, abrasion-resistant coating composition according to claim 1, wherein
The non-adhesive abrasion-resistant coating composition according to claim 7, which is the composition according to any one of (1) to (4). 9. A coated article having, as a top coat layer, a fired layer of a non-adhesive abrasion-resistant coating composition comprising an aqueous dispersion of melt-processable perfluoro-based copolymer particles, an organic filler and an inorganic filler. Wherein the amount of wear in the hot Taber abrasion test and the thrust abrasion test when measured under the following conditions are all less than 1 mg, and the surface of each coated article after the hot Taber abrasion test and the thrust abrasion test: Non-adhesive abrasion-resistant coated article having a contact angle with hexadecane of 40 ° or more. Serial to pure aluminum plate was roughened surface roughness Ra3μm by test coated article sandblasting, via a primer layer having a thickness of 10 to 15 [mu] m, the thickness 20~25μ as a top coat layer
m, a coated article having a fired layer of a non-stick, abrasion-resistant coating composition. Hot Taber Abrasion Test Using a heating type Taber abrasion tester, heat the abrasion wheel with the electronic copy paper fixed on its surface to 200 ° C. and rotate at 60 rpm.
m, with a load of 1 kg against the surface of the test painted article,
The process is performed until the top coat layer is worn and the primer layer is exposed. The evaluation is performed by measuring the weight of the test painted article every 1000 rotations based on the weight of the test painted article after the first 100 rotations, and averaging the weight loss (mg) every 1000 rotations. Thrust Abrasion Test Using a friction abrasion tester, a stainless steel abrasion wheel is rotated at a load of 700 g and a linear velocity of 200 mm / sec, and pressed against the coated article for 1 hour. The evaluation is made based on the weight loss (mg) of the test painted article at the end of the test. Using hexadecane contact angle surface contact angle meter, the hexadecane contact angle of each surface of the test coated article after the Taber abrasion test and each test coated article after the thrust abrasion test was measured at five points,
The average value is evaluated. 10. The non-adhesive wear-resistant coated article according to claim 9, wherein the non-adhesive wear-resistant paint composition is the composition according to any one of claims 1 to 4. 11. The non-adhesive wear-resistant coated article according to claim 9, wherein the top coat layer is formed on a metal substrate via a primer layer made of a fluororesin and a heat-resistant resin. 12. The non-adhesive abrasion-resistant coating according to claim 9, wherein the top coat layer is formed on a metal substrate via a primer layer composed of a fluororesin, a heat-resistant resin, and aluminum oxide powder. Goods.