Source: https://patents.google.com/patent/US7279260B2/en
Timestamp: 2018-05-20 14:46:54
Document Index: 633589511

Matched Legal Cases: ['arts\n2', 'arts\n1', 'arts\n1', 'art\n2', 'arts\n2', 'arts\n3', 'arts\n1', 'arts\n1']

US7279260B2 - Electrophotographic photoconductor having a crosslinked resin layer and method of preparing an electrophotographic photoconductor - Google Patents
Electrophotographic photoconductor having a crosslinked resin layer and method of preparing an electrophotographic photoconductor
US7279260B2
US7279260B2 US10458626 US45862603A US7279260B2 US 7279260 B2 US7279260 B2 US 7279260B2 US 10458626 US10458626 US 10458626 US 45862603 A US45862603 A US 45862603A US 7279260 B2 US7279260 B2 US 7279260B2
US10458626
US20040053152A1 (en )
The present invention further provides an electrophotographic photoconductor having a layer comprising a crosslinked silicone resin having —O—CH2—CH(OL1)-Z groups bonded to silicon atoms of said resin, wherein Z represents a charge transferability-imparting group and L1 represents a hydrogen atom or a bond connected to a silicon atom of said resin.
bonded to silicon atoms of said resin, wherein Q1 represents a hydrogen atom and Q2 represents an oxyalkylene group or an alkylene group, or Q1 and Q2 are taken in combination to represent a cycloalkylene group or a cycloalkylenealkylene group and L2 represents a hydrogen atom or a bond connected to a silicon atom of said resin, and —[O—CH2—CH(OL1)]p-Z groups bonded to silicon atoms of the resin, wherein Z represents a charge transferability-imparting group, L1 represents a hydrogen atom or a bond connected to a silicon atom of the resin and p is an integer of 1 or more.
heating the coating at a temperature of 80 to 150° C. to harden the coating.
(a) a silane compound having at least one an epoxy group and at least one hydroxyl group bonded to the silicon atom thereof;
In one specific embodiment of the first aspect of the present invention, the electrophotographic photoconductor has a resin layer containing a crosslinked silicone resin having —[O—CH2—CH(OL1)]p-Z groups bonded to silicon atoms of the resin, wherein Z represents a charge transferability-imparting group, L1 represents a hydrogen atom or a bond connected to a silicon atom of the resin and p is an integer of at least 1, preferably 2 or more. The charge transferability-imparting group is suitably an nitrogen-containing group.
wherein R26 represents a hydrogen atom, a halogen atom, an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents or an aralkyl group which may have one or more substituents, and X represents —O—, —S—, —SO—, —SO2—, —CO—, an alkylene which may have one or more substituents or an alkylene of the formula:
In the epoxy group-containing amine compounds of the above formula (1) above, the aryl group of the tertiary amino group-containing aryl group Ar1 may be the same as that described above in connection with the group R1. The tertiary amino group may be a group of the formula —X2—N(Ar5)(Ar6) where X2 represents a divalent organic group such as an alkylene group having one or more substituents, an alkenylene group having one or more substituents, an arylene group having one or more substituents and an aralkylene group having one or more substituents, and Ar5 and Ar6 independently represent an aryl group such as phenyl having one or more substituents.
The resin layer of an electrophotographic photoconductor according to the present invention may be a layer obtained by reacting a coating of a composition containing the above epoxy group-containing amine compound and the silicon compound. The reaction of the coating may be carried out by heating the coating at a temperature of at least 100° C. In this case, it is preferred that at least one of the alkoxysilane compound and the silanol compound has at least one group R which is an aromatic group for reasons of improving the uniformity and transparency of the resin layer. It is still preferred that the aromatic group-containing alkoxysilane compound and/or silanol compound be used in conjunction with an aromatic group-free alkoxysilane compound and/or silanol compound.
A coating of the above coating composition is dried to obtain a crosslinked resin layer. The drying conditions vary depending upon the kind of the solvent used, presence or absence of catalyst, etc., but are generally 60 to 160° C. for 10 minutes to 5 hours, preferably 80 to 150° C. for 20 minutes to 3 hours, more preferably 100 to 150° C. for 30 minutes to 2 hours, for reasons of formation of sufficient crosslinkages and prevention of thermal degradation of components of the resin layer.
—[O—CH2—CH(OL1) ]p-Z groups bonded to silicon atoms of the resin, wherein Z represents a charge transferability-imparting group, L1 represents a hydrogen atom or a bond connected to a silicon atom of the resin and p is an integer of 1 or more, preferably 2 or more.
In a reactor equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser provided with a trap to remove water formed during the reaction, 19.34 g (40.0 mmol) of 4-[2,2-bis(4-hydroxyphenyl)vinyl]phenyl-bis(4-methylphenyl)amine and 37.01 g (400.0 mmol) of epichlorohydrin are charged. The mixture was heated to 110° C. with stirring under a nitrogen gas stream. Then, while maintaining the mixture in the reactor at 100 to 120° C., 19.20 g (96.0 mmol) of a 10% by weight aqueous solution of sodium hydroxide were added dropwise to the mixture through 3 hours. During the reaction, epichlorohydrin emitted overhead from the reactor was condensed and returned to the reactor, while water was trapped and discharged from the system. After the addition of the sodium hydroxide solution had been completed, the reaction mixture was further reacted for 1 hour at 110° C. The resulting reaction mixture was allowed to cool to room temperature and epichlorohydrin was removed in vacuo. The remaining mixture was mixed with toluene and the organic layer was washed with water. The washed organic layer was then dried with anhydrous magnesium sulfate. The toluene was removed by distillation in vacuo to leave 20.75 g of a yellow crude product with a yield of 87.1%. The melting point of the crude product was in the range of 111.0 to 116.0° C. This was purified by column chromatography using a toluene/ethyl acetate (20/1 vol/vol) elution liquid and then recrystallized from ethyl acetate and ethanol to obtain 15.85 g (yield 66.5%) of an epoxy group-containing amine compound of the formula shown below as light yellow needle crystals having a melting point of 128.0-129.0° C.
measured: 80.80 6.33 2.37
calculated: 80.65 6.26 2.35
Wave Trans-
Number mittance
Peak No. (cm−1) (%)
1 3585.2 86.6961
2 3025.78 77.3751
3 3000.69 78.4534
4 2921.63 76.9159
5 2871.49 82.2575
6 1899.54 86.7041
7 1600.63 50.3127
8 1573.63 77.7945
9 1506.13 17.2425
10 1454.06 76.0974
11 1415.49 79.7039
12 1376.93 81.8354
13 1344.14 80.3811
14 1321.00 53.3842
15 1294.00 53.0009
16 1278.57 50.7674
17 1241.93 44.2706
18 1178.29 61.4308
19 1132.01 81.0636
20 1108.87 76.6790
21 1078.01 83.8241
22 1035.59 63.6697
23 970.019 83.2446
24 916.022 75.4043
25 862.025 77.7342
26 835.026 60.4030
27 815.742 57.3333
28 765.601 80.0271
29 736.674 78.7032
30 715.461 76.4214
31 659.536 76.4833
32 611.324 59.9646
33 451.261 2.62751
34 430.048 1.46642
Titanium oxide 400 parts
Melamine resin 40 parts
Alkyd resin 60 parts
2-Butanone 500 parts
Bisazo pigment of the formula shown below 12 parts
Polyvinyl butyral resin 5 parts
Charge transporting material 10 parts
1% Silicone oil tetrahydrofuran solution 1 part
A protective coating liquid (I) having the composition shown below was then spray-coated onto the charge transporting layer to form a protective layer having a thickness of about 3 μm and the resulting layered assembly was heated at 120° C. for 2 hours, thereby obtaining an electrophotographic photoconductor of the present invention.
Epoxy group-containing amine compound 4.2 parts
Methyltrimethoxysilane 5 parts
Phenyltriethoxysilane 5 parts
1% Aqueous acetic acid solution 5.57 parts
Tetrahydrofuran 30.7 parts
n-Butanol 3.67 parts
The precursor liquid was then heated at 60° C. for 2 hours with stirring for silanolizing the methyltrimethoxysilane and phenyltriethoxysilane by hydrolysis. The resulting liquid was mixed with 4.2 parts of the epoxy group-containing amine compound obtained in Synthesis Example 1 above to obtain a protective layer coating liquid (II). An electrophotographic photoconductor was then prepared in the same manner as that in Example 1 except that the protective layer coating liquid (II) was substituted for the protective layer coating liquid (I).
To a mixture composed of 21 parts of methyltrimethoxysilane and 21 parts of phenyltriethoxysilane, 8.16 parts of a 1% aqueous acetic acid solution were added through 25 minutes in an ice bath. The mixture was stirred at 5° C. for 30 minutes and then stirred at 24° C. for 2 hours for silanolizing the methyltrimethoxysilane and phenyltriethoxysilane by hydrolysis, thereby obtaining a hydrolyzed liquid.
Hydrolyzed liquid obtained above 3 parts
Epoxy group-containing amine compound 0.98 part
2-methoxyethyl acetate 2.62 parts
Cyclohexanone 2.42 parts
Tetrahydrofuran 0.98 part
Acetylacetone 0.12 part
Aluminum acetylacetonate 0.12 part
Hydrolyzed liquid obtained above 2.17 parts
Colloidal silica (average particle 2.32 parts
2-methoxyethyl acetate 1.9 parts
Cyclohexanone 1.63 parts
Acetylacetone 0.09 part
Aluminum acetylacetonate 0.09 part
An electrophotographic photoconductor was then prepared in the same manner as that in Example 1 except that the surface protective layer coating liquid (IV) was substituted for the protective layer coating liquid (I), that the application of the surface protective layer coating liquid (IV) was carried out by ring coating, that the applied coating of the surface protective layer coating liquid (IV) was allowed to stand at room temperature for 30 minutes and the resulting layered assembly was then heated at 130° C. for 1 hour, and that the thickness of the surface protective layer was 2 μm.
A protective coating liquid (V) having the composition shown below was then spray-coated onto the charge transporting layer to form a protective layer having a thickness of about 3 μm and the resulting layered assembly was heated at 120° C. for 2 hours, thereby obtaining an electrophotographic photoconductor of the present invention.
Epoxy group-containing amine compound 35 parts
3-Glysidoxypropyltrimethoxysilane 13 parts
Methyltrimethoxysilane 45 parts
Phenyltriethoxysilane 32 parts
1% Aqueous acetic acid solution 37.6 parts
Boron trifluoride triethylamine salt 0.5 part
Tetrahydrofuran 248.4 parts
n-Butanol 27.6 parts
The precursor liquid was then heated at 60° C. for 2 hours with stirring for silanolizing the 3-glysidoxypropyltrimethoxysilane, methyltrimethoxysilane and phenyltriethoxysilane by hydrolysis. The resulting liquid was mixed with 35 parts of the epoxy group-containing amine compound obtained in Synthesis Example 1 above and 0.5 part of boron trifluoride triethylamine salt to obtain a protective layer coating liquid (VI). An electrophotographic photoconductor was then prepared in the same manner as that in Example 5 except that the protective layer coating liquid (VI) was substituted for the protective layer coating liquid (V).
To 42 parts of glysidoxypropyltrimethoxysilane, 8.16 parts of a 1% aqueous acetic acid solution were added through 25 minutes in an ice bath. The mixture was stirred at 5° C. for 30 minutes and then stirred at 24° C. for 2 hours for silanolizing the glysidoxypropyltrimethoxysilane by hydrolysis, thereby obtaining a hydrolyzed liquid.
An electrophotographic photoconductor was then prepared in the same manner as that in Example 5 except that the surface protective layer coating liquid (VIII) was substituted for the protective layer coating liquid (V), that the application of the surface protective layer coating liquid (VIII) was carried out by ring coating, that the applied coating of the surface protective layer coating liquid (VIII) was allowed to stand at room temperature for 30 minutes and the resulting layered assembly was then heated at 130° C. for 1 hour, and that the thickness of the surface protective layer was 4 μm.
Hydroxyl group-containing amine compound 7 parts
Methyltrimethoxysilane 18 parts
1% Aqueous acetic acid solution 10 parts
n-Butanol 55.1 parts
Example of Thick- Obser- ΔVD ΔVL Image Formation
No. ness (μm) vation (V) (V) Quality of Cracks
1 2.9 A −30 +20 A A
2 2.7 A −30 +20 A A
3 0.80 A −30 +10 A A
4 0.65 A −20 +20 A A
5 2.9 A −30 +20 A A
6 2.8 A −30 +20 A A
7 0.7 A −30 +10 A A
8 0.5 A −20 +20 A A
Comp. 1 6.1 C −50 +30 B A
Comp. 2 5.5 B −10 +10 B C
Comp. 3 6.2 C −50 +30 B A
Comp. 4 6.0 C −50 +30 B A
wherein X1 represents a lower alkoxy group Y1 represents a ligand derived from a compound selected from the group consisting of M1COCH2COM2 and M3COCH2COOM4 where M1, M2, M3 and M4 independently represent a lower alkyl group, and n is an integer of 0 to 2, wherein the amount of ingredient (b) is such that the weight ratio (b)/((a)+(b)) of the ingredient (b) to a total amount of the ingredients (a) and (b) is in the range of 0.1 to 0.7.
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAGAI, KAZUKIYO;TANAKA, CHIAKI;SUZUKI, TETSURO;AND OTHERS;REEL/FRAME:014589/0492