JPH11286623A - Stain-resistant coating agent for recording devices - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating agent which can give a coating film excellent in thermal adhesion resistance, smoothness, and boiling water resistance by mixing a specified bisalkenyl-substituted nadiimide with a resin selected from a silicone resin, etc. SOLUTION: This agent comprises a resin component essentially consisting of a bisalkenyl-substituted nadiimide of the formula and at least one resin selected from a (modified) silicone resin, a polysulfone resin, a polyphenylene sulfide resin, and a fluoro resin. In the formula, R<1> and R<2> are each H or CH3 ; R<3> is -Cp H2p - (wherein p is 2-20), a 5-8C cycloalkylene, - (Cq H2q O)t (Cr H2r O)u Cs H2s }- (wherein q, r, and s are each 2-6; t is 0 or 1; and u is 1-30), a divalent 6-12C aromatic group, -(R)a -C6 H4 -R'- (wherein a is t; and at least one of R and R' is a 1-4C alkylene, or a 5-8C cycloalkylene), -C6 H4 -T-C6 H4 - wherein T is CH2 , C(CH3 )2 , CO, O, OC6 H4 C(CH3 )2 C6 H4 O, S, or SO2 }, or a group derived by replacing 1-3 H atoms of any one of these groups by at least one OH group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating agent which can be suitably used for painting or coating on parts requiring contamination resistance, such as OA equipment and printing machines. Used for recording equipment, excellent in stain resistance, excellent heat resistance adhesion, smoothness (sufficient hardness that does not scratch the coating), dynamic friction coefficient of a certain degree or more, and boiling water resistance and steam resistance (hereinafter, referred to as The present invention relates to a coating agent that forms a coating film that also has a "boiling water resistance".

[0002]

2. Description of the Related Art In a recording apparatus such as an electrophotographic printer, a copying machine, a facsimile and an ink jet printer in OA equipment, printing machines, etc., in particular, a part which contacts when a printing paper passes is a toner. If they are contaminated by ink or ink, they will re-adhere to the printed matter,
Coatings on these parts must be stain resistant, as they hinder obtaining high quality printed matter. Conventionally, the coating or coating of a recording apparatus that requires such contamination resistance is made of a fluororesin or a fluororesin that has excellent cleaning properties and can easily remove attached substances such as toners and inks by wiping. A coating agent comprising a silicone resin, a modified silicone resin or a polysulfone resin, or a coating agent comprising a silicone resin, a modified silicone resin and a silicone oil has been widely used.

[0003] However, there has been a problem that a film formed by using a fluororesin has poor heat-resistant adhesion, and requires an undercoat because of insufficient adhesion to a base. Furthermore, with the recent technological innovation, the parts used for the paper feed part are required to have a smooth surface (sufficient hardness to prevent the coating from being damaged) in order to respond to higher printing speeds.
Components used around the spraying step of a water-resistant treatment agent for increasing the water resistance of printed matter have also been required to have boiling water resistance, but the smoothness and resistance of the conventional stain-resistant resin as described above have been increased. Boiling water was not enough.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional stain-resistant resin, to further increase the stain resistance, and to cope with recent technical innovations in recording apparatuses. An object of the present invention is to provide a coating agent capable of forming a film having excellent heat adhesion, smoothness (high hardness), a coefficient of kinetic friction of a certain level or more, and boiling water resistance.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object of the present invention, and as a result, a coating agent based on an alkenyl-substituted nadimide and containing a specific resin has been cured. The present invention has been completed by finding that a coating film having excellent stain resistance, excellent heat adhesion, smoothness (high hardness), dynamic friction coefficient and boiling water resistance to a certain degree or more is obtained.

That is, the gist of the present invention is that (A) the general formula [1]

Embedded image [Wherein, R ^1, R ² are each independently selected hydrogen or a methyl group, R ³ is -C _p H _2p - (Here, p is 2 to 20
Alkylene group represented by an integer), a cycloalkylene group of _{C 5 ~C 8, - {(} C q H 2q O) t (C r H 2r O) u C s H
_2s ｝-(where q, r, and s are each independently selected 2
6 integer, t is an integer of 0 or 1, u is a polyoxyalkylene group represented by an integer) from 1 to 30, a divalent aromatic group _{C 6 ~C 12, - (R} ) a -C ₆ H ₄ —R′— (where a is an integer of 0 or 1, and R and R ′ are at least one independently selected from a C _{1 to} C ₄ alkylene group or C ₅
-C ₈ cycloalkylene group)
Phenylene group or an alkylene-phenylene-alkylene _{group, -C 6 H 4 -T-C} 6 H 4 - { However, T is -CH _{2
-, - C (CH 3)} 2 -, - CO -, - O -, - OC 6 H 4
A group represented by C (CH ₃ ) ₂ C ₆ H ₄ O—, —S—, —SO ₂ —｝ or a group in which 1 to 3 hydrogens of these groups are substituted with a hydroxyl group] An alkenyl-substituted nadimide;
(B) a stain-resistant coating agent for a recording device, which comprises, as an essential resin component, at least one resin selected from a silicone resin, a modified silicone resin, a polysulfone resin, a polyphenylene sulfide resin and a fluororesin. Exist.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin composition of the present invention will be described in more detail. Examples of the bisalkenyl-substituted nadimide of the component (A) used in the coating agent of the present invention include JP-A-59-80662 and JP-A-60-80662.
No. 178,862, Japanese Unexamined Patent Application, First Publication No. Sho 61-188761,
A known alkenyl-substituted nadimide described in JP-A-63-170358 and the like, Japanese Patent No. 2729565
Various alkenyl-substituted nadimides according to the formula (1) can be used and generally have the general formula [1]:

Embedded image [Wherein, R ^1, R ² are each independently selected hydrogen or a methyl group, R ³ is -C _p H _2p - (Here, p is 2 to 20
Alkylene group represented by an integer), a cycloalkylene group of _{C 5 ~C 8, - {(} C q H 2q O) t (C r H 2r O) u C s H
_2s ｝-(where q, r, and s are each independently selected 2
6 integer, t is an integer of 0 or 1, u is a polyoxyalkylene group represented by an integer) from 1 to 30, a divalent aromatic group _{C 6 ~C 12, - (R} ) a -C ₆ H ₄ —R′— (where a is an integer of 0 or 1, and R and R ′ are at least one independently selected from a C _{1 to} C ₄ alkylene group or C ₅
-C ₈ cycloalkylene group)
Phenylene group or an alkylene-phenylene-alkylene _{group, -C 6 H 4 -T-C} 6 H 4 - { However, T is -CH _{2
-, - C (CH 3)} 2 -, - CO -, - O -, - OC 6 H 4
A group represented by C (CH ₃ ) ₂ C ₆ H ₄ O—, —S—, —SO ₂ —｝ or a group in which 1 to 3 hydrogens of these groups are substituted with a hydroxyl group] Alkenyl substituted nadimides are used. The bisalkenyl-substituted nadimides are generally synthesized by the reaction of the corresponding alkenyl-substituted nadic acids or their acid anhydrides with diamines.

As the bisalkenyl-substituted nadimide represented by the general formula [1], N, N'-ethylene-bis (allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide), N, N'-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) ), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylbicyclo [2 2.2.1] Hept-5-ene-
N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) wherein the diamine is an aromatic diamine ), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2 2.1] Hept-5-ene-2,3-
N, N'-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 wherein the diamine is <alkylene.> Phenylenealkylenediamine -Dicarboximide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
N, N '-(o-phenylene) methylene-bis (allylbicyclo [2.2.1] hept-) in which the diamine is an alkylene phenylenediamine
5-ene-2,3-dicarboximide), N, N'-
(P-phenylene) ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Of course, the compounds exemplified herein are those in which the allyl group is replaced by a methallyl group, or one of the compounds exemplified above and those mentioned above, in which one hydrogen atom of the norbornene ring is substituted by a methyl group. Compounds may also be exemplified as compounds that can be used in the present invention.

These bisalkenyl-substituted nadimides may be used alone or as a mixture of two or more.
These bisalkenyl-substituted nadimides may be used as oligomers. In the present invention, “bisalkenyl-substituted nadimide” is used in a sense including its oligomer.

[0011] The silicone resin of the component (B) used in the coating agent of the present invention, a modified silicone resin,
As the polysulfone resin, the polyphenylene sulfide resin and the fluorine resin, various known resins can be used. Specific examples thereof include a methylpolysiloxane resin, a methylphenylpolysiloxane resin and a methylhydrogenpolysiloxane resin as silicone resins, and an epoxy-modified silicone resin, a polyester-modified silicone resin, and an acryl-modified silicone resin as modified silicone resins. And polysulfone resins such as phenol-modified silicone resins, polysulfone resins,
Examples of fluororesins such as polyarylsulfone resins and polyethersulfone resins include polytetrafluoroethylene resins, tetrafluoroethylene / perfluoroalkylvinyl ether copolymers, tetrafluoroethylene / hexafluoropropylene copolymers, tetrafluoroethylene / hexa Examples include fluoropropylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, and the like. These resins of the component (B) may be used alone or in combination of two or more.

In the coating agent of the present invention,
The content of the bisalkenyl-substituted nadimide of the component (A) can be arbitrarily selected according to the desired physical properties of the coating film obtained by curing the coating agent. Is suitably 10 to 90% by weight based on the total weight of the bisalkenyl-substituted nadimide of the component (A) and the resins of the component (B). If the proportion of the bisalkenyl-substituted nadimide as the component (A) exceeds 90% by weight, the heat-resistant adhesion of the generally obtained coating film is undesirably reduced depending on the type of the component (B), and if it is less than 10% by weight. The effect of adding the bisalkenyl-substituted nadimide as the component (A) is not sufficiently recognized.

In the coating agent of the present invention, in addition to the above-mentioned essential resin components (A), the bisalkenyl-substituted nadimide and the resin (B), carbon black and metal Color pigments such as oxides and pigments such as extender pigments such as barium sulfate, talc and mica powder can be appropriately blended. The mixing ratio of these pigments is 5 to the total weight of the essential resin components.
0% by weight or less is appropriate. If it exceeds 50% by weight, the effect of stain resistance is reduced. Also, if necessary, a dispersant,
An anti-settling agent, a plasticizer, and other additives generally used in paints and coating materials can be appropriately compounded.

The coating agent of the present invention is prepared by adding the above essential resin component and, if necessary, a pigment and other additives by any method and, if necessary, using toluene, xylene, butyl cellosolve, N-methyl- What is necessary is just to mix uniformly using 2-pyrrolidone and naphtha. In general, it is prepared by stirring and manufacturing with a disper or dispersion manufacturing with a sand mill.

The method of using the coating agent of the present invention is generally such that the surface of the article is coated with the coating agent by any method such as air spray coating or dip coating, and then the coating agent is cured by heating. It is performed by That is, by heating at a temperature of 80 to 420 ° C., preferably 120 to 400 ° C., for 0.005 to 2 hours, preferably 0.005 to 1 hour, it cures to form a coating. In addition, a cured film may be used, if necessary.
By performing post-curing treatment at 0 to 350 ° C. for 0.5 to 1 hour, a stronger film can be obtained.

The material of the article to which the coating agent of the present invention is applied is not particularly limited as long as it can be used in the developing section, the fixing section and the periphery of the recording apparatus, and is suitable for both engineering plastics and metals. Excellent stain resistance, heat resistance, smoothness and boiling water resistance.

[0017]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 to 12 and Comparative Examples 1 to 4 As a bisalkenyl-substituted nadimide, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximido) phenyl @ methane (manufactured by Maruzen Petrochemical Co .; BANI-M; hereinafter, abbreviated as "BANI-M");
A methylphenylpolysiloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; KR-311; hereinafter abbreviated as "silicone KR311") as a silicone resin, and an epoxy-modified silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .; ES-) as a modified silicone resin.
1001, hereinafter abbreviated as “Silicone EP”), a polyester-modified silicone resin (Cold Schmidt; Silicophthal HTL, hereinafter abbreviated as “Silicone ES”), and a polysulfone resin as a polyether sulfone resin (Sumitomo Chemical Co., Ltd .; PES-5003P) , "P
ESR), polyphenylene sulfide resin (manufactured by Toray PPS, Inc .; M3910, hereinafter “PPSR”)
), A polytetrafluoroethylene resin (manufactured by Hoechst Japan; TF-9205, hereinafter abbreviated as “PTFE”) as a fluororesin,
Perfluoroalkyl vinyl ether copolymer (manufactured by Du Pont-Mitsui Fluorochemicals; MP-10, hereinafter referred to as "PF
A) and a dispersant (Kusumoto Kasei Co., Ltd .; Dispalon # 1860, hereinafter abbreviated as "Disparon")
With toluene, butyl cellosolve and N-
After using methyl-2-pyrrolidone (hereinafter abbreviated as "NMP") at a ratio (% by weight) shown in Table 1 for 1 hour with a disper for stirring or for 2 hours with a sand mill, a general air spray gun is used. Was used to paint the test plate. As shown in Table 1, the types of test plates are an aluminum plate, a polyamide imide (hereinafter abbreviated as “PAI”) plate, a polyether ketone (hereinafter abbreviated as “PEEK”) plate, and a polyether imide (hereinafter abbreviated as “PEI”). ) Plate, polyphenylene sulfide (hereinafter abbreviated as “PPS”) plate, polyether sulfone (hereinafter abbreviated as “PES”) plate, and liquid crystal polyarylate (hereinafter abbreviated as “LCP”) plate,
Their size is 150 x 70 x aluminum plate
0.8 mm, others are 150 × 70 × 5 mm. After painting, the test plate was dried at 100 ° C. for 10 minutes,
The coating was formed by heating and curing at 30 ° C. for 30 minutes, and the stain resistance, heat-resistant adhesion and boiling water resistance were examined by a predetermined method. Table 1 shows the results.

In the table, the evaluation of the stain resistance was performed on the toner and the ink as follows. A toner (manufactured by Canon; code F41-8601-00) was applied to the prepared coating.
0, for GP-30F) to spread and adhere
Baking was performed at 0 ° C. for 1 hour, and the mixture was allowed to cool to room temperature. First, the degree of detachment of the toner was visually determined by applying slight vibration, and then the surface was wiped with a cloth to visually determine the degree of detachment of the toner. The evaluation was based on the average of three tests. ◎ indicates that the toner was almost completely released by only the first slight vibration, は indicates that the toner was completely released by wiping with a cloth, and △ indicates that the toner was removed even after wiping with a cloth. X indicates that adhesion was slightly observed, and X indicates that toner adhesion was clearly observed even after wiping with a cloth. As for the ink, an ink (manufactured by Canon; code F47-0951-500, BJI-201BkH)
C) was added dropwise until it spread to a diameter of about 30 mm, dried by heating at 150 ° C. for 1 hour, allowed to cool to room temperature, and after wiping the surface with a cloth, it was visually determined whether or not ink stains had adhered. . Evaluation is based on the average of three tests.
Indicates little dirt, ○ indicates slight dirt, △
Indicates that the stain is visible but not conspicuous, and x indicates that the stain is well understood.

The heat-resistant adhesiveness is measured according to JIS K5400 as to the adhesiveness to a material when heated at 200 ° C. for 100 hours.
8.5.2. Are evaluated by the cross-cut tape method of No., ◎ indicates 10 points, ○ indicates 8 points, Δ indicates 6 points, and × indicates less than 6 points.

The evaluation of the boiling water resistance was performed in the same manner as described above by immersing the produced coated article in boiling water for 100 hours and then using a grid tape method.

The pencil hardness, which is an index of the smoothness of the coating, is expressed by J
IS K5400 8.4.2. The coefficient of kinetic friction was determined according to JIS K7125, using PPC paper as a mating material, a sliding distance of 50 mm, a sliding speed of 300 mm / min, a load of 214 g, and a measurement atmosphere of 23.
It measured at 50 degreeC and 50% RH.

[0023]

[Table 1]

From these results, it can be seen that the coating agent having the bisalkenyl-substituted nadiimide BANI-M shows good stain resistance, heat resistance, boiling water resistance and smoothness.

Examples 13 to 20, Reference Examples 1 and 2 and Comparative Examples 5 to 8 N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene as a bisalkenyl-substituted nadimide And methylphenylpolysiloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; TSR145; hereinafter, "silicone") as a silicone resin. TSR ”and KR-220, hereinafter abbreviated as“ silicone KR-220 ”), silicone EP as a modified silicone resin, and P as a polysulfone resin.
ESR, each resin of PTFE as a fluororesin, silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .; KR-96, hereinafter abbreviated as "silicone oil"), and carbon black as a coloring pigment (manufactured by Asahi Kasei Corporation; black 3078, hereinafter referred to as "C")
B3078 "and carbon black # 45 (hereinafter abbreviated as" CB45 "), manufactured by Mitsubishi Kasei Kogyo Co., Ltd., and barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd .; precipitated barium sulfate # 100; hereinafter referred to as" barium sulfate ") as an extender. Abbreviated), talc (manufactured by Nippon Talc Co .; talc MS, hereinafter abbreviated as “talc”) and mica powder (manufactured by Yamaguchi Mica Industrial Co., Ltd .; mica A-1,
(Hereinafter abbreviated as "mica powder") and an anti-settling agent (RHEOOX)
Inc. Manufactured by Benton 27, hereinafter abbreviated as "anti-settling agent") using disparone as a dispersant, naphtha, butyl cellosolve and NMP as a solvent in a sand mill for 2 hours or 3 hours at a ratio (% by weight) shown in Table 2. After dispersion manufacturing, aluminum plate, PAI plate, PEEK plate, PEI plate, PPS using a general air spray gun
The plate, the PES plate, and the LCP plate were coated on those shown in Table 2. After drying these at 100 ° C. for 10 minutes,
The coating was formed by heating and curing at 200 ° C. for 30 minutes, and stain resistance, heat resistance adhesion and boiling water resistance were examined in the same manner as in Examples 1 to 12 and Comparative Examples 1 and 2. Table 2 shows the results.

[0026]

[Table 2]

From these results, it is understood that the coating agent containing the bisalkenyl-substituted nadiimide BANI-X exhibits good stain resistance, heat-resistant adhesion and boiling water resistance.

[0028]

EFFECTS OF THE INVENTION The coating agent of the present invention is less susceptible to adhesion of toner, ink and the like than a conventional fluororesin, a coating agent obtained by blending another resin with a fluororesin, or a silicone resin. Excellent stain resistance,
In addition, it provides a cured product having excellent heat resistance, boiling water resistance, smoothness, and a certain level of dynamic friction coefficient, and is particularly useful for painting or coating of a recording apparatus.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 183/04 C09D 183/04 (72) Inventor Fumitaka Yoshioka 1109 Shibaide, Kuramochi-cho, Nabari City, Mie Prefecture

Claims (3)

[Claims] (A) General formula [1] [Wherein, R ^1, R ² are each independently selected hydrogen or a methyl group, R ³ is -C _p H _2p - (Here, p is 2 to 20
Alkylene group represented by an integer), a cycloalkylene group of _{C 5 ~C 8, - {(} C q H 2q O) t (C r H 2r O) u C s H
_2s ｝-(where q, r, and s are each independently selected 2
6 integer, t is an integer of 0 or 1, u is a polyoxyalkylene group represented by an integer) from 1 to 30, a divalent aromatic group _{C 6 ~C 12, - (R} ) a -C ₆ H ₄ —R′— (where a is an integer of 0 or 1, and R and R ′ are at least one independently selected from a C _{1 to} C ₄ alkylene group or C ₅
-C ₈ cycloalkylene group)
Phenylene group or an alkylene-phenylene-alkylene _{group, -C 6 H 4 -T-C} 6 H 4 - { However, T is -CH _{2
-, - C (CH 3)} 2 -, - CO -, - O -, - OC 6 H 4
A group represented by C (CH ₃ ) ₂ C ₆ H ₄ O—, —S—, —SO ₂ —｝ or a group in which 1 to 3 hydrogens of these groups are substituted with a hydroxyl group] An alkenyl-substituted nadimide;
(B) A stain-resistant coating agent for a recording device, comprising, as an essential resin component, at least one resin selected from a silicone resin, a modified silicone resin, a polysulfone resin, a polyphenylene sulfide resin and a fluororesin. 2. The stain-resistant coating agent for a recording apparatus according to claim 1, wherein the content of the bisalkenyl-substituted nadimide is 10 to 90% by weight based on the total weight of the essential resin components. 3. The stain-resistant coating agent for a recording apparatus according to claim 1, wherein the coloring pigment and / or extender pigment are contained in a proportion of 50% by weight or less based on the total weight of the essential resin components.