CA1095642A - Electrophotographic sensitive layer - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
An electrophotographic sensitive layer comprising a new soluble photoconductive resin containing an aromatic tertiary amino group of the following formula as a photoconduc-tive functional group wherein ? represents a benzene nucleus containing at least one nitrogen-free electron donating substituent, C1 represents a carbon atom on the aromatic ring, and C2 represents a carbon atom which forms a hyerocarbon residue and takes a bond orbit of the SP2 or SP3 type;
and the benzene nuclei represented by ? are bonded to each other through a methylene group to such an extent as to maintain the solubility of the resin.

Description

~ his invention relates to a very useful electro-ph~tographic sensitive layer containing a soluble photo-conductive resin as a photoconductive material.
The soluble photoconductive resin is characterized by containing an aromatic tertiary amino group of the following formula as a photoconductive functional group ~C/ \C2-- ............. (1) ~ . :
wherein ~ represents a benzene nucleus containing at least one nitrogen-free electron donating mlclear substituent, Cl represents a carbon atom on the aromatic ring, and C2 represents a carbon atom which forms a hydrocarbon residue and takes a bond orbit of the S~ or SP3 type;
and the benzene nuclei represented by ~ are bonded to each other through a methylene group to such an ex*ent as to maintain the solubility of the resin.
Office copying by electrophotographic methods has become very widespread in recent years, and on the other hand, various attempts have been made to develop other uses that depend on the various characteristics of the electrophotographic methods. Some of these attempts have already resulted in commercially acceptable applica-tions such as microfilms, microfiches, second masters for engineering drawrings~transparent sheets for overhead projectors, slides for slide projectors, and radiography.

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The conventional electrophotographic methods used for office copying are roughly divided into a coated pa~er copying process (CPC for short) and a plain paper copying process (PPC for short). ~he former comprises forming a toner image directly on paper coated with a photoconductor and fixing it as such, and the latter comprises first forming a toner image on the surface of a photoconductor, then transferring it to plain paper, and fixing the image transferred. Generally, the CPC process has the advantage that a copying machine of simple structure can be used and the resulting image has good qualityO ~ut since the copy-B ing paper is coated with ~n~ oxide as a photoconductor,it is inconvenient to handle, and the resulting copy is heavy. On the other hand, the PPC process requires an apparatus of a complicated structure which is expensive.
But since copying can be made on plain paper, the resulting copy has an appearance close to printed matter and thus gains a popular acceptance of the userO For this reason, the PPC process has become prevalent.
In the other applications mention abo~e, however, the CPC process is frequently desirable or even essential :
from the standpoint of the quality of the images obtained, the desired size of the images, and the cost of image-forming machines. In addition, in many cases, it is necessary to use plastic film bases instead of paper, and 1~ ~
plastic film and paper bases for such uses are frequently required to be transparent or translucent. Zinc oxide 1: .
' previously used mainly in the CPC process is non-transparent, a~d cannot be applied to such uses. It can be app~eciated :

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therefore that in order to apply electrophotography to such uses other than office copying, a photoconductive composi-tion having transparency and flexibility and usable as a thin photosensitive layer on paper or a film is a very important key materialu Inorganic photoconductors are un~uitable for this purpose, and organic photoconductors become absolutely necessaryu Investigations have been actively conducted in this field both on low-molecular-weight compounds and on high-molecular-weight compounds, but have been unable to provide photoconductors having entirely satisfactory utility such as the ease of use and cost in addition to good sensitivityO
It is an ob~ect of this invention therefore to provide an electrcphotographic sensitive layer contain-ing an organic photoconductor which is suitable for use as a photosensitive layer on a base such as film or paper, : very easy to prepare, cheap, and easily shapable into a thin film by coating on the base and has sufficiently feasible sensitivity.
lt is known that aromatic tertiary amines . ~ containing a unit of the formula C3 (Ia) ~ 25 ~ C / \ C ~
`~ , 1 2 ~
wherein Cl is a carbon atom on an aromatic ring, and C2 and C3 represent carbon atoms forming a :
. ~ , .
.... ~ .
- .. . ., . ~ . . ~ , .

~09~i~42 hydrocarbon residue and taking a bond orbit of the Sp2 type or SP~ type, exhibit good photoconductivity preferably when com~ined with a suitable sensitizer. r~ypical e~amples of such amines are N-~substituted carbazoles and substituted aniline derivativesO
Previously, the following three typical methods ha-~e been used to form electrophotographic photoconductive layers using compounds containing an aromatic tertiary amine unitO
(I) A lower-molecular-weight compound of a definite structure such as N-butyl carbazole is uniformly dissolved in a suitable high-molecular-weight compound to form a photosensitive layer, as di~closed in United States Patent 3,206,~06.
(II) As seen in the case of notable poly-N-vinylcarbazole, a polymer having a recurring unit of ~; formula (Ia) above is prepared from a monomer containing a unit of formula (Ia) or its precursor unit, and the polymer is fabricated into a thin film form to make a ~
photosensitive layer.
(III) As in the case of the reaction between ,:
polyepichloropydrin and a carbazole alkali salt disclosed n Japanese ~aid-Open Patent Publication No. 97,540/7~, a polymer is reacted with a low-molecular-weight compound to introduce a unit of formula (la) as a pendant group of the polymer.
According to method (I), a large amount of the low-molecular-weight photoconductive material is required _ 5 _ i '' :' , : - . - , , ~ .

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in order to obtain sufficientl~ feasible sensitivityO It is very seldom however that the low-molecular-weight photo-conductive material can form a stable mutually dissolved sys1,em wi-th a binder polymer added to impart film-forming ability. ~ven when a stable system can be formed, it fre-quently undergoes phase separation or blooming and its quality changes, unless it is stored carefully as a photosensitive materialO
In the case of method (II), the above-mentioned poly-N-vinylcarbazole and its substituted derivatives are considered to have best properties, and some of them are accepted commerciallyO However, since polymers of this : kind are prepared through two steps of monomer synthesis and polymerization and the purification of the product in each step is strictly required in order to obtain feasible properties, the resulting polymers are generally very expensive, and can be used only in very limited applicationsO
'According to method (III), however, the polymer and the low-molecular-weight compound used in a polymer reaction are both commercially available at low cost, If they can be converted to a photoconductive polymer having good properties by a simple reaction, it will be obvious that there is a possibility of providing an electro-; photographic sensitive layer having excellent utility and ; 25 being free from the defects inherent to the methods (I) and (II) described aboveO
In order that the electrophotographic sensitivelayer may have sufficient sensitivity, it is necessary to introduce a photoconductive group in an amount above a ,. .
' ~gSG~2 certain limi.t. In order to achieve this introduction with-out; causing undersirable side-reactions such as gellation, the polymer and the low-molecular-weight compound must react selectively with each other with good reactivityO
Actually, it is very difficult to find out combinations meeting these requirements from commercially utilizable polymers and low-molecular-weight compounds~ In spite of many attempts, none have yet been accepted commerciallya ; We therefore made investigations in order to find out photoconductive resins containing units of the type (la) which can be obtained by a method following the method (III) described above and has excellent utilityO ~hese investigations led to the discovery that the aforesaid resins containing the unit of formula (1) meet these requirements r We first noted that soluble aromatic formaldehyde resins containlng an electrophilic reactive group such as a methylol or dimethylol ether ~roup, as typified by a xylene/
: formaldehyde resin or a resol resin are readily available as the trunk polymerO These resins are not the high-molecular-weight c~ain polymers used in the conventional method (III), but rather oligomers. We also noted that ~; as the low-molecular-weight compounds, aromatic amine compounds of the following formula : 25 H
Ar-~-N ~ Y )n wherein Ar is an aromatic group, the group -~-N - Y)n is bonded to the carbon atoms7 of the aromatlc ring, n is 1 or 2, and Y is a '.
'. : .

56'~2 hydrocarbon residue which optionally forms a ring with ~r either directly or through a nitrogen, oxygen or sul~ur atom with the proviso that when n is 1, Y may be a hydrogen atom, such as carbazole, dip~lenylamine, aniline or methylaniline, are commercially available at low cost, and that the hydrogen atom bonded to the nitrogen atom in the above compound undergoes a substitution reaction wi.th the electrophilic reactive group and ;s substituted by à group of the benzyl type thereby to $orm a unit of formula CIa) which is introduced into the polymer.
The present invention provides an electrophotographic -sensitive layer ~hich comprises:
(11 at least one solvent-soluble aromatic amino-containing photoconductive resin as a photoconductive base;

(2) at least one sensitizer selected from the group consisting of optical sensitizers and chemical sensitizers; and (.32 at least one solvent-soluble binder polymer having compatibility with said solvent-soluble aromatic amino-containing photoconductive resin (12; said solvent-soluble aromatic amino-containing photoconductive resin (1) being a reacti.on product o~ (i2 a soluble low-molecular-weight poly-condensate comprising a xylene/formaldehyde resin or a resol-type phenolic resin ~ith (ii2 an aromatic amino compound of ~ the formula ; H
(.2) Ar~N-Y~n H
wh.erein Ar is an aromatic group, the group ~N-Y2n is bonded to the carbon atoms of the aromatic ring, n is 1 or 2, and Y is a hydrocar~on residue which optionally forms a ring with Ar a~

l~S~
either directly or through a nitrogen, oxygen or sulfur atom;
and when n is 1, Y may be a hydrogen atom; said polycondensate having a molecular weight of 200 to 3,000 and having dimethylol ether groups, methylol groups and/or functional groups thereof, the content of said groups being one per Q.l to 3 benzene rings of said polycondensate, said reaction product containing, bonded to the benzene ring, as pendant groups, at least one N-methylene aromatic amino group of the formula CH
1 2 (4) Ar~N-Y)n CH
wherein Ar is an aromatic group, the group ~N-Y~ is bonded to the nuclear carbon atom of the aromatic group, n is 1 or 2, and Y is a hydrocarbon residue or a hydrogen atom and optionally forms a ring together w~th Ar either directly or through a nitrogen, oxygen or sulfur atom, or is optionally bonded to the benzene ring through a methylene group at a rate of at least one per 0.5 to 7 benzene rings, said N-methylene aromatic amino group being selected from the following group:

Cl H2 Cl H2 Cl H2 I H2 ,~
~3 ~ 2~5 ~ ~2 N lH2 and N ~
:

g _ . . :
, .

~s~z

3 ~ NHCH3.

The soluble aromatic tertiary amino-containing photoconductive xe5in used as a photoconductive material of the photosensitive layer in accordance with th.is invention can be prepared from the polycondensate (il and the aromatic amine compound ~.il, hoth.easily available commercially, by a simple procedure, fox example, in the simplest case by merely mixing them and heating the mixture. Since thi.s. photoconductive re5in h~s superior cha~acteristics .' .
, :

~ : -9a-.

1()~5642 to be described below, it can provide a photosensitive layer having excellent utilityO
Unlike the low-molecular-weight compound used i.n the method (I) above, the photoconductive resin is a glass-like transparent resin having film-forming ability, and can form a photosensitive layer without using a binder polymex~ When a photosensitive layer having better flexibility is desired, a binder polymer can be added~
~he amount of the binder polymer can, however, be very : 10 small as compared with the case of the method (I). Further-; more, unlike the case of the method (II) which involves mutually dissolving a high-molecular-weight aliphatic poly-; mer and another polymer, a very wide range of binder polymers are available for complete mutual dissolution with the photoconductive resin since its molecular weight is about that of oligomers although it is a polycondensateO Hence, according to the desired end use, a stable, transparent thin film-like photosensitive layer can be formedO
Furthermore, the photoconductive resin used in this invention surprisinglY has better sensitivity than a model compound having defin.ite structure in spite of the ( .
fact that because of the method of its preparation, its structure cannot be represented by definite repeatin~ unitsO
It has already been confirmed experimentally, as will be ehown later in a comparative example, that for example, a composition of a polycondensate of a xylene resin and carbazole, a typical example of the photoconductive resin used in this invention, has far higher sensitivity than a composition of N_benzylcarbazole, a model compound ~ . , :

.
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having the same photoconductive functional group, when the same sensitizer and the same binder are incorporated i.n the same amountsO The same result is obtained when the sensitivity of a composition of a poly-condensate of xylene resin and aniline is compared with that OL a composition of dibenzylaniline, a model compound of the former~
In view of the ease of preparing the photo-conductive resin used in this invention, the latitude of compounding recipes for preparation of a photosensitive layer and its better sensitivity than model compounds owing to its particular structure, it will be readily appreciated that the present invention can afford an electrophotographic sensitive layer having excellent utilityO
The electrophotographic sensitive layer of this invention can be formed even from the photoconductive resin alone. But in certain uses, the sensitivity of such a sensitive layer is low and its flexibility is insufficientO
In many cases, therefore, it is preferred to incorporate suitable amounts of sensitizers and binding polymersO
~he sensitizers, from the standpoint of their ; function, can be classified into optical sensitizers (or dye sensitizers) and chemical sensitizers Where a high sensitivity is required, both types of sensitizers are frequently used together. In special cases, a substance which concurrently acts both as a binder polymer and as a chemical sensitizer can be used.
~ he photoconductive resin, the sensitizers, the binder polymers and the photosensitive layer will be described in detail below citing preferred examplesO

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1. Photoconductive resin (1-1) Soluble low-molecular-weight polycondensate The soluble low-molecular-weight polycondensate used to prepare the photoconductive resin can be obtained by reacting a benzene-type com-pound containing at least one nitrogen-free electron donating nuclear sub-stituent and at least two nuclearly substituted hydrogen atoms capable of methylol substitution by formaldehyde, with formaldehyde and/or its func-tional derivative in a manner known ~ se to cause addition-condensation.
The addition-condensation should be carried out to an extent sucb that the resulting low-molecular-weight polycondensate is solvents soluble and pref-erably also fusible.
Suitable benzene-type compounds for preparing the soluble low-molecular-weight polycondensate are expressed by the following formula (A)Q tA')Q.

~ CH2(CH2)m]r ~ ) (3) wherein Q, Q' and r are positive integers, m is 0 to ~, [Q + q X r] is 1, 2, 3 or ~; Q' is 0 or 1, and when q is 0, ~ ~ represents [ CH2 ( OCH2 )m] r --W ~ q a~ hydrogen atom; r is 0 or 1, and wben r is 0, the benzene ring C is directly bonded to the nuclear carbon atom of the benzene ring B; and A and A' are identical or different and represent at least one group selected from the class con-sisting of alkyl groups containing 1 to carbon atoms, alkoxy groups containing 10 g S 6 ~ Z

1 to 4 carbon atoms, a hydroxyl group and halogen atoms~ with the proviso that when ~or ~' is 2 or more, A and A' may be different groups selected from the above class, and at least one of A and A' should be an electron donating group selected from the above class.
Examples of such benzene-type compounds include toluene, xylene, diphenylether, butylphenylether, phenol, cresol, xylenol, t-butylphenol, anisole, isopropylbenzene~ tri-methylbenzene, ethylbenzene, l-butylbenzene, p-phenylphenol, trimethylqlylbenzene, pseudocumene, and dureneO 0f these, xylene, diphenyletherg phenol or substituted (e.g~, halogen-or alkyl-substituted) phenol are preferredO m-Xylene is especially preferred because it is sl~bstantially colorless~ ~-~he formaldehyde and/or its functional derivatives are used mainly in the form of formaline, but also in the form of paraformaldehyde, trioxane or chloromethylmethyl etherO
~he reaction between the benzene-type compound 20 ~and formaldehyde and/or its functional derivatives is carried out by a suitable known method according to a given combination of the reactants~ Naturally, ;t is not suf~flclent to merely obtain a polycondensation product, but care should be taken so that a reactive group capable of participating in a reaction with the aromatic amine compound of formula (2), that is, a methylol group or its functional derivative expressed by formula (l-C) or formula (l-B) wherein m is not less than 1, should remain in a sufficient amount.

,. .
' - ' '~' ' ' .: , . . -iO~ 642 In the case of a benzene-type com~ound which reacts mainly as a difun~tional compound is a methylolation reaction, such as m-xylene, pseudocumene or durene, a soluble resin containing a methylol group, a dimethylol ether li~kage, etc~ in addition to a methylene linkage can be obtained by subjecting the ben~ene compound and an excess amount of formaldehyde in the form of formalin or trioxane to addition-condensation in the presence of an acid catalystO
On the other hand, in the case of a benzene-type compound which reacts mainly as a trifunctional compound in a methylolation reaction~ such as phenol or cresol, a soluble resi~ containing a reactive methylol group of the so-called resol type can be obtained by reacting it with formaldehyde in the presence of an alkali catalystO
A benzene-type compound which is relatively dif-ficult to methylolate, such as diphenylether, is chloro-methylated with a mixture of hydrochloric acid and trioxane, : a mixture of formalin, hydrochloric acid and sulfuric acid, :: : or chloromethyl ether to form a resinous product~
~he chloromethyl group could be used as a kind of:a:functional derivative of methylol group~ Generally, however, it is preferably converted to a methylol group or~dimethylol ether linkage by hydrolysis, or to an alkoxy-methyl group by alcoholysis, or to an acyloxymethyl group 25 ~by esterification prlor to reaction with the aromatic amine compound of formula (2)o mis is preferred because corrosive hydrogen chloride does not form during the reactionO
Especla]ly preferred polycondensates are a xylene : resin~using m-xylene, modified xylene resins, a diphenyl `~:
` - 14 _ :

!,` ~ ~

,: ' , :
,'' , ' . ' ' either resin, and resol-type phenolic resinO "Nikanol"
(trademark for a product of Mitsubishi Gas Chemicals, Co~, Ltd~) having an oxygen content of 3 to 18,~ and a softening point (in the liquid state at room temperature) of up to 150C is suitable as the xylene resin of modified xylene resin. On the other hand, paint resins that cure on baking are suitable as the resol-t-~pe phenolic resinO
Generally, these resins preferably have a high -content of a methylol group, a dimethylol ether group, and~or their functional derivatives because they react with the aromatic amine compound in a great ratioO However, if the content of these reactive groups is too large, a cross-linking reaction occurs competitively at the time of the reaction between the soluble low-mole-cular-weigh-t poly-condensate and the aromatic amine compound, and theproduct would become insolubilizedO In order, therefore, to maintain the solubility of the photo-conductive resin of this invention, the content of these reactive groups ; ~ ~ should be adjusted to a sultable range according to the 20 benzene nuclei constituting the aromatic amine compound ; .
of formula (2) or the soluble resinD ~he xylene resins are especially preferred in this regard since they do not :
:substantially undergo a cross-linking reaction even when r ~ containing a large amount of reactive groups, and are less colored than phenolic resinsO
GeneralIy~ the soluble low-molecular-weight polycondensates have a molecular weight of 200 to 3,000, an~ their content of a dimethylol ether group, a methylol i , group and/or its ~unctional derivatives is one per Ool to j ~'~
~.. : .
.~. ~ `, . , :

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3 benzene nucleiO
Since one dimethylol ether group can react with two HN' groups as schematically shown below, its content, calculated as methylol group, is regarded as 2, -CH2CI~?- + HN~ > -C~2N~ + uoC~ _ `NH + HOCH2- ~ CH N- + H 0 (1-2) Aromatic amine compound ~ he aromatic amine compound used to prepare the photoconductive resin is expressed by formula (2).
Preferably, the aromatic grou~ Ar in the formula contains 1 to 2 benzene or naphthalene nuclei containing 6 to 15 carbon atoms as an aromatic ring, and especially consists mainly of 1 to 2 such benzene groupsO The carbon atoms on the aromatic ring may, for example, contain 1 to 3 sub-stituentsO Preferred substituents are alkyl groupscontaining 1 to 3 carbon atoms, alkoxy groups containing 1 to 3 carbon atoms7 aryloxy groups containing 6 to 10 carbon ato~s, N,N'-disubstituted amino groups, and halogen groups.
A part (preferably not more than ~0 mole/0) of Ar can contain a strongly electron attracting substituent such as a nitro, cyano or alkoxycarbonyl groupO But when a greater part of Ar contains such a group, it adversely affects the photo-conductivity of the resulting resin, and therefore, such a large content of substituent is not preferredO ~hen Y
l5 an aromatic group, the same requirements for Ar and the same preferred examplès as described above are applicable.
Ar and Y may be bonded to each other and form H
1 to 2 aromatic fused multi-nuclei together with ~~~a Preferred examples are carbazole, phenoxazine, and indoleO
~ .

:

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When Y is other than an aromatic group~ it is preferably a hydrocarbon group containing 1 to 10 carbon atoms which may contain the same substituents as described above with re~,ard to ArO As in the case of indoline, for exampleO
Ar and Y may be bonded to each other to form a fused multi-nucleus, as described aboveO Especia]ly preferred examples of the hydrocarbon group are lower alkyl groups containing 1 to 3 carbon atoms and a benzyl groupO
Specific examples of preferred aromatic amine compounds are given below. -(a) When n=l, and Y=H:_ Aniline, toluidine, xylydine, p-ethylaniline, p-chloroaniline, p-bromoaniline, 2,4-dichloroaniline, p-., .
anisidine, o-anisidine, ~i,N-dimethyl-p-phenylenediamine, :~ :
l 15 and a- or ~,-naphthylamine.
(b) When n=l, and Y is not an aromatic group . :
and is not bonded to Ar~
: N-methylaniline, N_ethylaniline, N-propylaniline, N-benzylaniline, N-methyltoluidine, N,N,N'-trimethyl-p_ phenyl~enediamine, N-cyclohexylaniline, and N_methyl_x-naphthylamine.
(c) When~n=l, and Y is an aromatic group but not bonded to Ar:-Diphen~lamine~phenyl naphthylamine, d1naphthyl-2~5~ amine~ dit~oluylamine:, and 4,4'-dichlorodiphenylamineO
d) When n=l and Y ls bonded to Ar:-Carbazol~e7~ 3-chlorocarbazole, 3,6-dibromocarbazole~

ndole,~isoindole,~indo1ine,~phenoxazine, phenothiazine, :and~:2-phenylbenzimidazole~

. ~
~ 17 -` ~ :
.

.:
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(e) When n=2:-

4,4'-bis(monomethylamino)-diphenylmethane 7 4,4'-bis(monoethylamino)diphenylmethane, 1,lr4,~'-bis (monomethylamino)-diphenyl]ethane, 4,4'-bis(monobenzyl-amino) diphenylmethane, 4,4'-bis(phenylamine)diphenyl-methane, 4~4'-bis(methylamino)-triphenylmethane, N,N'_ dimethyl-p-phenylenediamine, N,~'-diphenyl-p-phenylenediamine, N,N'-(~-naphthyl)-p-phenylenediamine, and diindole.
Preferred aromatic amines are those which are easily melted together with the soluble polycondensate and can react in the molten state. But in order that they may be readily available and afford photoconductive resins of reduced coloration, they are especially preferably those - -of formula (2) in which Y is selected from the group consist-ing of a hydrogen atom, lower alkyl groups, a benzyl group, and a phenyl group, specifically at least one of aniline, toluldine, N-methylaniline, N_ethylaniline, N-benæylaniline, carbazole, diphenylamine, and 4,4'-bis(methylamino) diphenylmethaneO
20 ~ he~above aromatic amine compounds are limited to~those ln whioh~l to 2 hydrogen atoms ate bonded to nitroge~ atom of the amino group. This is because whe~ they contal~nl3 or more such hydrogen atoms, the~
easlly~reaGt witil the reactive groups of the soluble 1QW-

5~ molècular-wei~ght polycondensate, and the reaction product ~ undergoes~gellatlon and~becomes insolubleO Some oP the ~ ` ~ ;;~ aromatlc amine~compounds, however, give improved sensiti-ty or~fllm_~orming~ab-lllty when a part (generally not ¦ ~ ~more~than 30 molè/0) oP them is replaced by an aromatic ,'~

,: -, . ~ . . - , , : .

~oss64z amine compound in which at lel~t 3, preferably 3 to 4, hydrogen atoms are bonded to the amino group. ~xamples of such aromatic amine compound are 4,4'-diaminodiphenyl-methane, 4,4 ~- diaminodiphenyl ether, and p- or m-phenyl-enediamineO(1-3) Co_condensation component ~ h~ utility of the photoconductive tertiary amino-containing resin can sometimes be improved further for certain applications by using a co-condensation component which reacts with the reactive groups of the polycondensate to the same degree as the aromatic amine compound in the preparation of the above photoconductive resinO ~he co-condensation component includes, for example, polynyclear aromatic hydrocarbons and phenolic compounds. ~he poly-nuclear aromatic hydrocarbon sometimes has an effect ofincreasing the sensitivity of the photoconductive resin, ,but since it is susceptible to coloration, it is properly ¢hosen according to the desired usage. Preferred phenolic compounds are those containing at least 3 aromatic rings, ~20 ~such~as anthracene~ perylene, or phenanthrene. ~he anth-J;~: r~acene is~especially preferred~ The mixing mole ratio of~the polynuclear aromatic hydrocarbon to the aromatic amine compound is generally 001-3 : 1, preferably 0.1-1 : 1.
The phenolic compound as a co-condensation com-;25~ ponent~sometlmes has an effect of improving film-forming abl~lity of the photoconductive resin and the compatibility of~the aromatlc amine compound wlth the binder polymerO
Preferred phenolic compounds are phenol, o-cresol, m-cresol, p-cresol, mixed~cresol,~3,5-xylenol, and t-butylphenolO

. .~ ~

~1 ' .
, , .

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The mixing molar ratio of the phenolic compound to the aromatic ami.ne compound i.s generally 0.1-3 : 1, preferably 0.1-1 : 1.
(1~4) Preparation of the photoconductive tertiary a~i.no-containing resin It i~ known to some extent that a tertiary amino-containing resin can be obtained by condensation between the soluble lOw-molecular-weight polycondensate and the aromatic amine compound, as in the case of a reaction of aniline with a xylene-formaldehyde resin disclosed, for example, in K, 0: Kogyo Kagaku Zasshi 58, 520 (1955) and 62, 129 (1959). However, it has been unknown that the reaction of the soluble low-molecular-weight poly- .
condensate with a secondary amine of a diarylamine type such as carbazole or diphenylamine yields a tertiary amine preferentially, and thus gives a resin containing it.
. ~he novel soluble aromatic tertiary .
: amino-containing resin of this invention is prepared by reacting (1) a soluble low-molecular-weight polycondensate ::
: obtained by addition-condensation of a benzene compound : 20 containing at least one nitro~en-free electron donating n~uclear:~substltuent and:at least:two nuclearly substituted hydrog~en ~atoms capable of methylol substitution by forma}dehyde, wlth formaldehyde and/or its functional derivatlve~ in which at least~:one of the benzene compound resl~ues~contains a p~endant group of the following formula -CH2X ~ C) :wherein~X lS a h;~droxyl group, an alkoxy group, an 0-acyl~grou~p or a:halogen atom, as~a~substituent bonded to the carbon atoms of the benzene _ 20-? ~: :

' ' ' ' . ' , ~ ' , . . .' ....... . . .
.. . ~ .
. . ' ' ' ' ~ . ' ' . ' , . . ' ' ' ' . , ~og56~2 ring in principle, with (2) an aromatic amine compound of the following formula Ar~ Y ) (2) whe ein Ar is an aromatic group, the group -~ N~Y)n is bonded to the nuclear carbon atom of the aromatic group9 n is 1 or 2, Y is an aromatic group which i 5 identical with or : different from Ar or optionally forms a ring either directly or through a nitrogen, oxygen or sulfur atom, thereby to substitute the methylene group bonded to the carbon atom of the benzene ring for the .hydrogen atom bonded - .-to the nitrogen atom forming the amino group of the aromatic amine compound (2), and has good photoconductivity~
~he ratio between the low-molecular-weight poly condensate (1) and the aromatic amine compound (2) used for preparing the photoconductive resin is in principle such that the conten.t of the dimethylol ether group, the methylol group and/or their functional derivative of the polycondensate (l)~is equal in equivalent weight to the content of the h~drogen atoms bonded to the nitrogen atom of the amino group, and in many cases, this ratio is preferred. It s not necessary however to a~just the ratio exactly to this standard, but accordin.g to the desired purposes, the ;25 ratio can be otherwiseO For example, when it is desired to increase the amino group content of the photoconductive resin as much as possible, it is sometimes preferred to employ a method in which the aromatic amine compound (2) is fed in excess so that the dimethylol ether group, the _ 21 -`' : ~
, , . ~ . . , ~0956~2 methylol group e~d/or their fwlctional derivatives of the polycondensate (1) may be used in the reaction with the amino group of the aromatic amine compound (2) as completely as possible, and after the reaction~ the excess unreacted amine (2) is removed from the resulting photoconductive resin by distillation or re-precipitation~ In this case, the amoun-t of the aromatic amine compound (2) is generally 20 mole% to ~00 equivalent% excess.
In some case, the aromatic amine compound (2~
is charged in an amount smaller than the eguivalent weight in order that a part of the dimethylol ether group, the methylol group and/or their functional derivatives of the polycondensate (1) may be used in a substitution reaction with the ring carbon atoms of the aromatic amine (2) with or without the carbon atoms of the benzene ring of the poly-; condensate (1) in addition to being used in the reaction with the amino group of the amine (2), thereby to increase the molecular weight of the resulting photoconductive resin and to improve its softening point or film-forming ability.
I~, howe~er, the amount of the aromatic amine compound fed is too small, the proportion of the photoconductive group of the photo-conductive resin decreases to cause a reduction in sensitivity. Furthermore, this tends to cause the gellation of the resulting resin by crosslinking as during the reaction. Generally~ therefore, it is preferred to use the aromatic amine compound in an amount at least half the equivalent weight~
Depending upon the tgpe of the aromatic amine compound (2) and the reaction conditions, the dif~erence _ 22 -:

~.. . :
:,: . . : - ~, - -.
. .

lOgS64~ :

between the substitution-reactivity of the reactive groups ~of the polycondensate (1) with the hydrogen atom bonded to the nitrogen atom of the amino group and that with the hydrogen atoms bonded to the nuclear carbon atoms on the aromatic nucleus sometimes becomes small, and the aforesaid gellation tends to occur. Hence, care is sometimes required in choosing the amount of the aromatic amine compound (2) and the reaction conditions~
~ ~he reaction between the polycondensate (1) and ; 10 the aromatic ~mine compound (2) is promoted b~ using a catalyst. Generally, the catalyst is preferably an acid catalyst such as m-xylenesulfonic acid, methanesulfonic acid or toluenesulfonic acid. ~he amount of the catalyst is generally 0.001 to 20%~ preferably 0.1 to 2%, based on the weight of the soluble low-molecular-weight polycondensate (2). ~he reaction can be carried out in the presence of an inert reaction solvent such as nitrobenzene or methyl benzoate. However, since it is necessary to separate the result m g photoconductive resin from the solvent after the reactlon,~ it is generally advantageous to perform the reactlon~in~the molten state while evaporating off the by-product water or if desired, evaporating off the unwanted unreact~ed~reaotion components. Preferably, the reaction s performed in an atmo~sphere of an inert gas such as 25~nltrogèn or argon ln order to prevent the coloration of the~resùltlng resln by~oxidation. In some cases, the reactlon can~be carrled out at reduced pressure.
; The react~ion of the aromatic amine compound (2~
with the polycondensate (1) with or without the cocondensation 23 _ .:
.;~ :

, . ~ , . ' - : . .

1~)9564Z

co~ponent is carried out at a temperature of generally 50 to 300C, preferably 120 to 230Co The reaction time var:ies according to ther conditions such as the reaction temperature, but i5 generally 002 to lO hours, pre.~erably l to 4 hoursO
~ he state of progress of the reaction can gene-rally be traced by measuring the NMR spectrum or IR
spectrum of the reaction mixture~ In the case of the NMR spectrum, it can be confirmed by the state of the dis-lO appearance of an absorption ascribable to the proton of :-`NH in the aromatic a~ine (2 ) and an absorption ascribable to the proton of -CH20- i.n the aromatic amine (2) with the progress of the reactionO In the case of the IR spectrum, it can be confirmed by the reduction of a characteristic absorption ~scribable to the stretching vibration of the bon.d of ~N-Ho Sometimes, it is se~-? b~r ~n infrared absorption spectrum, for example, that even after the reaction, a proton of the ,NH type slightly remains in the resulting resin~ This is presumably because the reaction of the methylol ~ 20 group and/or its functional derivatives with the carbon :~ ~ atoms on the aromatic ring of the aromatic amine (2) takes place competitivelg with the reaction of such groups with the -NH_ group, and consequentl~, the _NH group partly remains in the resin, or a group of the benzyl type is .
~ 25 rearranged from the tertiary amino group formedO
i`~ ; After the reaction, the resin formed can be used as a photoconductive resin composition for an electrophotographlc sensitive layer without particularly purif~ing it but if desired, after adding a sensitizer , _ 24 -.. . . .
. .

~09564Z

or a binder resin of the type~ already described.
~ he resulting resin can, if desired, be purified~
for example, by dissolving it in a solvent such as methyl ketone or chlorobenzene and pouring the solution into a non-solvent for the resin such as methanol to remove the unreacted matter, or by reducing the resulting resin to a powder or granule, and extracting it with a substance which is a non-solvent for the resin but a solvent for the unreacted materials (e.g., methanol) to remove the unreacted materials.
It is also possible to introduce a suitable amount of halogen into the aromatic group of the resulting resin by contacting it with a halogenating agent for substituting a halogen atom for the hydrogcn atom on the aromatic ring, for example, bromine, chlorine, N-bromosuccinimide or 9ul-furyl chloride; or by reacting it with oleum to introduce a nitro group into a part of the aromatic group.
These resins subjected to post reactions can be used egually to the above-mentioned reslns, and are included within the definition of the photoconductive tertiary amino-containlng resins specified in the present invention.
5)~ Properties of the photoconductive tertiary amino-containing resin he photoconductive resin obtained by the process 2~5 descr~be~d above is a transparent amorphous solid resin which s colorless or colored~generally to blue, green, yellow or brown. It has a softening point of 50C to a point at ;;which it becomes infusible. Preferably, it has a softening point of 70 to lsoa. The resin is soluble in a wide range ., '' `

.

10956~2 of organic solvents, and can be cast into fil~s from its solutions in these solventsO Preferred solvents are those having a boiling point of 40 to 200C, for example, ketones such as methyl ethyl ketone, acetone, methyl : :
isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene and ~Jlene, halogenated hydrocarbons such as dichloromethane, tetrachloroethane and chlorobenzene, ethers such as tetrahydro ~ran, dibutyl ether and anisole, esters such as ethyl acetate and butyl acetate, and amides 10 such as dimethyl formamide, dimethyl acetamide and N-methyl- ~-pyrrolidone .
~he photoconductive resin used in this invention ~.
generally has a molecular weight, in terms of an inherent viscosity determined at 30C for a solution of the resin in N~methylpyrrolidone in a concentr~tion of 0O5 g/100 ml., ~:of 0.03 to 0.80, pre~erably 0.07 to 0O50O ~he amino group content of the resin is preferably 1 per 0.5 to 7 benzene nuclei forming~the soluble polycondensate (1) and especially ~;1 per 0.6 to 4 benzene nucleiO
20;~ his amino group is bonded to th~ benzene ring forn~g:the skeleton~of (1) in the ~orm represented by the~following formula Ar--~-- N _ Y) (4) 2~5 ~ whereln~Ar lS an aromatio group, the group Y) is bonded to the carbon atom of the ;~ aromatlc ring, ~ is 1 or 2, and Y is a hydrocarbon residue or a:hydrogen atom, !:
~ 2~ -,, ' `: :

'',:. ~, ~ :
' ' ~ ,: : , .

10~56~Z

and optionally formc a ring together with Ar either directly or through a nitrogen, oxygen or sulfur atom~ or is optionally bonded to the benzene ring B or C in formula (3) through a methylene groupO
~he amino group content can generally be deter-mined easily by calculation from the nitrogen content of the photoconductive resin of this invention measured by an elemental analysisO
Sometimes, amino groups other than the tertiary amino groups mix in the photoconductive resinO As stated hereinabove, the amount of such other amino groups can be determined, for example, by an infrared absorption spectrum or NMR spectrumO Since the photoconductive resin of this invention contains various kinds of tertiary amino groups, l it is difficult to determine the amount of the tertiary :1 ~ amino groups directlyO For example, the proton in ,N- ~ detected by an NlYR spectrum is an effective l~ ~ t~ol for determinationO A suitable method, such as an in- .
i~ ; 20~ frared absorption spectrum or mass spectrum, should be chosen ac~cordlng to the photoconductive resin obtained. Generally, a~method relying~on elemental analysis is simple and convem ent, and~widely applicableO An ultraviolet ab:sorption spectrum:and an ultraviolet visible fluorescent 25 ~spectrum can also o~fer:effective means of identifying the co~mpoundsO
(2) : : Sensitizers : In many cases, it is preferred to add a sensi-:tizer to the electrophotographic sensitive layer~o~ this 'I ~

` ~:

.
. : : - . .

lOg~64Z

invention in order to increase the sensitivity of the photo-conductive amino-containing resin as a photoconductive materialO Such sensitizers can be classified into optical senAsitizers and chemical sensitizersO ~hese two types 5 of sensitizers can be used alone to produc~ an outstanding ~-sensitizing effect, but preferably used togetherO
(2-1) Optical sensitizers ~ he optical sensitizers absorbs light having a longer wavelength than the sensitive wavelength limit of a main photosensitizer and transfers its energy to the -photosensitizer thereby to excite the photosensitizer.
~his broadens the sensitive wavelength region of the photo-sensitizer to increase the proportion of that portion of the light from a light source which is utilized for sensi-'15 tization, ~nd thus to increase the overall sensitivity of the photosensitizer. Usually, dyes having an absorption in the visible region can be used as the optical sensitizers.
In many cases, the optical sensitizers are effecti~e even when added in very small amountsO
20 ~ In the present inve~tion, known optical sensitizers !: :
for organic photoconductors can be used. Specific examples of pr~ePerred optical sensitizers are described below.
(a) ~rlarylmethane-type compounds Crystal Vlolet, Victoria Blue BH, Victoria Pure 25~ Blue~BOH~, Methyl Violet Pure Special, Malachite Green, Dianlx Blue EB-E, Diacryl ~urquoise Blue BG-E, Dianix Bril_ liant Red BS_E, Dlacelliton Fast Pink R, Acid Violet 5B, t`'~ SoIar Cyanine ~B, Acid Violet 6B, Brilliant Green, Methy~
Violet, Victoria Blue 6B, and Bictoria Blue 6B9 and Victoria , .
i: .':
:

. .
, . . . - 1 . .

lOgS6'~Z

B]ueO
(b) Anthraquinone-type compounds 4,5-Dinitrochrysazin~ L~,8-dinitroanthraquinone9 1,5-diaminoanthraquinone, 1-amino-2-phenoxy-4-hydroxy-anthra~uinone, l-methylamino-anthraquinone, ~urquoise Blue 776, Kayaset Blue 985, and Kayaset Blue 020.
(c) Cyanine-type compounds 3,3'_Diethyl_2,2'-thia-oxacarbocyanine iodide, 2-(p-dimethylaminostyryl)-3-ethyl benzothiazolium iodide, 1-carboxymethyl-1'-carboxyethyl-2,2'-quinocyanine bromide, ; and 1,1'-dlethyl-2,4'-quinocyanine iodide.
(d) Rhodamine-type compounds Xhodamine B, Rhodamine 6G, Rhodamine B Extra, and ~ulfo-Xhodamine B.
(e) Xanthene_type compounds L Rose Bengal and ~rythrosine.
(f) Thiazine-type compounds Methylene Blue.
(g) Acridine-type compounds o~ Acridine Yellow and Acridine Orange.
~;:
(h) Quinoline-type compounds Cryptocyanine and pinacyanol.
~ (i) C rbonyl-type compounds L`~ Alizarin and Solway Ultrablue B~
25~ rom the standpoint of effects, dyes of the tri~arylmethane type are preferred. Dependi~g upon the absorption wavelengths of these dyes, two or more of the optical sensitizers can be used in order to broaden the , .
absorption areaO

- 29 _ -` ~ ' ' . ", .... . .. : .

Some specific co]ors are undersired in certain uses of the photosensitive layer. Generally, blue to violet dyes having an absorption wavelenKth in the yellow to red regions are conveniently used from the standpoint of efficiency and appearanceO Examples of these sensitizers are Crystal Violet, Kayaset Blue 985, and Victoria Pure Blue BOH. ~he amount of the optical sensitizer is usually O.OOOlto 20% by weight, preferably 0.01 to 15% by - weight, based on the weight of the photoconductive resin.
(2-2 ) Chemical sensitizers The chemical sensitizer increases photoconductivity by chemically reacting with a main photosensitizer during non-exposure and/or during exposure to facilitate the generation of carriers by light Or the movement of such carriers.
Compounds heretofore known to be effective for the photoconductor containing a tertiary amine unit of formula (Ia) for example can generally be used as the chemical sensitlzers in~the present invention. Preferred chemical 0~ sens~itiZers are those which can ~ix with the photoconductive res~ln~as a maln~photosensitizer to an extent of at least 0.1 %~by~weight, preferably at least 1% by weight. These compounds can be~divided roughly into compounds having the~propertles of an electron acceptor and halogen-5~ p~ontaim ng~organlc;~co~ oundsO ~he former include ~ewisaclds~ln the broad sense, and are preferably those o~apable~o~Porml~ng a charge-transfer complex with the aromatic amines (2)o Accordingly, compounds based on aro-matlc~ compounds oontaining an electron attracting sub-sbltuènt, such~as benzene, naphthalene, anthracene~

~ 3 ~

, i,:

~ ~,... ., , . ' . ., ,', " ' .- , : ' ' 109S6~

fluorene, fluorenone or biphenyl are generally preferredO
~xamples of the electron attracting group are a nitro group, a carboxyl group or its derivatives, a c~ano group, a halogen group, a sulfone group, a ketone group, an aldehyde group, and a sulfonic acid group or its derivatives.
Chemical sensitizers having at least 1, preferably 2 to 4, electron attracting groups are preferredO
0f the above-exemplified substituents, the nitro group is preferred because of its great electron attracting propertyO However, polynitro compounds are generally colored, and many of them are strongly colored especially when forming a charge-transfer complexO In certain applications, this coloration may pose a problem. In such a case, a carboxyl group and its derivatives such as an anhydride group or ester group, and a cyano group are preferred. ~hese compounds, either of high or low molecular weight, can be used if only they meet the require-ment of compatibility with the photoconductive resin. ~hus, aromatic nitro compounds, aromatic carboxylic acid or the derivatives thereof, and arometic cyano compounds can be used as chemical sensitizersO
xamplles of the aromatic nitro compounds are trlnitrofluorenone, tetranitrofluorenone, (2,4,7-trinitro-9-fluorenylidene) malononitrile, nitroanthracene, di-; 25 ~nitroanthracene, trinitroanthracene, nitroanthraquinone, ; dinitroanthraquinone, trinitroanthraquinone, o- or m-dinitrobenzene, dinitronaphthalene, nitrophenol, dinitrophenol, trinitrophenol, mononitrocatechol, dinitro-catechol, monochloro-mononitrophenol, monochlorodinitrophenol, : ~ , .
- .
.
.
.

1~)95642 mononitrocresol, and dinitrocresolO
~ xamples of the aromatic carboxylic acids or their derivatives include phthalic acid, tetrachlorophthalic acid, tetrab~omophthalic acid, trimellitic acid, pyromellitic acid, naphthalene 1,8- or 2,~-dicarboxylic acid, benzo-phenonetetracarboxylic acid, anhydrides and esters of these acids, nitrobenzoic acid, dinitrobenzoic acid, trinitro-benzoic acid, monochloro-mon~trobenzoic acid, monochloro- ' dinitrobenzoic acid, and dinitronaphthoic acid. Generally, 10 the sensitizing effect becomes greater in the order of the ~'- ' ' ' esters, the acids~ and the anhydrides, and therefore, the anhydrides are most preferred.
~xamples of the aromatic cyano compounds are -isophthalonitrile, phthalonitrile, 4-nitrophthalonitrile, tetracyanobenzene, and nitro benzonitrile.
~ etracyanoquinodimthane, tetracyanoethylene, chloranil, dichloroacetic acid, and maleic anhydride can i, .
~ also be cited~ ~
t~ Especially preferred chemical sensitizers are 20~trinltrof1uorenone,; nitrobenzoic acld, nitrochlorobenzoic acid,~nitrophenol,~dinitrophenol, nitrochlorophenol, ':
phenol,~phthalle anhydride, trimellitic anhydride, aphthalene-1~8-ldicarboxylic anhydride, naphthalene~
4~,5,~ etracarboxy1ic acid, and naphthalene-1,4,5,8-tetra-25~ carb ~ ic~dianhiydride. ~
he senSitlzlng mechanism of the halogen-containing compound is not;clear, but~it is~presumed that a halogen "~ radioa~l dlsqoclated by the~dlrect or indirect action of ght wlll pla;y~an~lmportant roleO Compounds containing '` ' ~. ' :

.

~og5642 at least one carbon-halogen bond in the mole cule and meet the requirement of compatibility are chemically stable while dark at room temperature whether they are left alone or in the presence of the photoconductive resin or binder polymers. If these compounds can general halogell radicals on exposure, they can be used as chemical sensitizers ; in this invention irrespective of their molecular weight.
Preferably, the halogen in these compounds is chlorine, bromine or iodineO Chlorine and bromine and especially preferredO In view of the compatibility with the photocon-ductive resin and the sensitizing effect, aromatic halogen compounds, especially halogenated phenol and its derivatives, ` are preferred~ Examples of these preferred species are halogenated bisphenols such as 2,2'-methylene-bis(4-chloro-phenol), 2,2'-methylene-bis(7~,4,6-trichlorophenol), 4,4'-methylene-bis(2-chlorophenol), and 4,4'-isopropylidene-bis(2,6-dibromophenol), mono-, di- or trichloro phenol, mono-, di- or tribromo phenol, chlorocresol, and halogenated phenolic resins formed between halogenated phenols and formaldehydes.
xamples of other halogen-containing compounds that can be used in this invention are polycarbonates or copolycarbonates derived from the above-exemplified ;halogenated bisphenols, epoXy resins containing the above 2~5~halogenated bisphenol units, products obtained by adding the halogenated bisphenols to ethylene oxide or pro-pylene oxide to form glycols, polyesters derived therefrom, halogenated phenyl esters of polyacrylic acid or polyme-,: ~
thacrylic acid, copolymers of such a unit with other vinyl ~ .
.
' ' .' :: .

~ogs6~2 monomers, and hexachloro-p- or m-xyleneO Other useful halogen-containing compounds include9 for example9 polyvinylidene chloride, polyvinyl chloride, polyvinyl bro-mide, copolymers containing these as a partial recurring unit, and halogenated paraffin compounds such as pentaery-thrityl bromideO
Of the above-exemplified compounds, polymers can b~ used concurrently as binder polymers to be describedO
We have found that polyarylmethane compounds of the following formula R / ~ ~ ~

wherein Rl to R4 are identical or different, and represent an alkyl, alicyclic or aralkyl group containing 1 to 7 carbon atoms, and R5 represents -at least one of alkyl, alicyclic, aryl and aralkyl : :
groups containing 1 to 7 carbon atoms, and 20~ - ~ ~ Rl , R6 and R7 are identical or 7 P' different and represent a lower alkyl group containing l to 3 carbon atoms or a halogen ;25~ groups, and p and p' represent an integer of 0 to 2, have~an outstanding sensitizing effect on the photo-conductlve resins containing carbazole or its nUcleus-substitut : ~ ~ ed derivatives,although their sensitizin~ mechanism is not ~ : : ' `
~ 34 -.
: `
::

, ~ : ' . .

1~56~Z

entirely clear~
~ hese compounds themselves contain a unit of formula (Ia) and become photoconductive when combined with the halogen-containing organic compounds described aboveO
But when they are combined with the photoconductive resin containing carbazole, they produce a very good sensitizing action even in the complete absence of the halogen-contain-ing organic compound as sensitizer.
'~he chemical sensitizer must be added in a larger amount than the optical sensitizer in view of its action. ~he amount of the chemical sensitizer differs according, for example, to the proportion of the photocon- -ductive group of type (Ia) in the photoconductive resin or the molecular weight of the sensitizer, but is generally 0.1 to 100/o by wei~ht, preferably 1 to 70% by weight, based on the weight of the photoconductive resin.
When the amount of the chemical sensitizer is too ~small, its effect is reduced, and on the other hand, when it exceeds a certain limit, the effect no longer increases~
0~ urthermoré~ since the addition of the chemical sensitizer generally aggravates the properties of the photosensitive ayer~as a coatlng, it~is preferred to determine the most feasible a un-t experimentally according to the desired use.
(iii) Binder polymers 25~ he photoconductive resin used in the photo-sensitive layer of this invention has film-forming abl~lty,~bllt in many cases, its molecular weight is not so~high. In order therefore to obtain a photosensitive ayer having superlor flexibility, it is frequently necessary i:.: :

:

. ~: . . . .
. , to add a binder polymerO
Generally, with increasing amount of the binder re~sin, the sensitivity of the photosensitive layer some~/hat decre~ses in many casesO T.he amount of the binder polymer should desirably be as small as necessary.
Gen.erally, the amount of the binder polymer is ~0.05 to 1.5 parts, preferably Ool to 1 parts, based on the weight of the photoconductive resin.
Preferably, polymers used for this purpose are . 10 well soluble in at least one of the good solvents for the photoconductive resin which are described hereinabove. ~ny : . :
of polycondensates, pol~-addition type polymers, ring- ..
opening polymerized polymers and vinyl type polymers can be used for this purpose so long as they have a softening i15 point of at least 60C, can form films h~ving superior : flexibility and are compatible with the photoconductive resin to an extent at least to give translucent films.

à, ~Examples of suitable binder polymers are poly-condensates, for example, amorphous saturated copolyesters : 20~derlved from an acid component such as terephthalic acid, ~ ..
sophthallc acid, phthalic aeid or adlpic acid and a glycol component~such as ethylene glycol, propylene glycol, ` neop~entyl glycol or~tetrameth~lene glycol, oil-modified alky~d resins,bisphe~nal A type polycarbonates and phenoxy resins, ~` 25~ and e:poxy reslns,::p~olyad~dition-type polymers such as polyure-thane~resin conta:inin~ aliphatic polyesters as a solft se~ment, vl~nyl-type~polymer~s~such as polystyrene, polyacrylates, ~t.~pQly~thaorylates, polyvinylacetate, polyvinyl chloride, an~ copolymers contalnlng any of these as one component, j: . ~ ` . :

1:

~.^` -. ~` , .. .

~og5642 and ring-opening polymerized polymers such as polyepichloro-hydrin. For certain applications, the phtosensitive layer is required to be transparent~ In such a case, it is necessary to choose resins which have particularly good compatibility. As stated previously, some of the halogen-containing polymers concurrently act as sensitizers. These binder polymers can be used in combination of two or more.
(iv) Preparation of electrophotographic sensitive layer Generally, the electrophotographic sensitive layer of this invention is prepared by dissolving predetermined amounts of the photoconductive resin with or without the sensitizer and the binder polymer in an organic solvent, coating the resulting solution on a support, and then dry-ing ito For certain applications, finely divided silica, for example, is added in order to impart graphic properties or a mat finish to the photosensitive layer.
~ he dissolution of the above components in solvent can be performed either by dissolving a mixture of these component, or dissolving these components in optional order in a solvent, or dissolving them separately and mixing the resulting solutions. ~he suitable concentration of the ; solute of~ the solution differs according to such factors ; as~the type of the~solute components, or the method of coating, but generally, 5 to 80% by weight, preferably 10 t ~ to 60% by weight.
he method of coating the resulting coating solution on a support ma~ be any method capable of forming a uniform photosensitive layer. Generally, wire `~

~ 37 -~ ,: . .
`

.
~ ..... . . , : ;
, . . , ~ . .

lOgS64Z

bar coating~ knife coating, Wheeler coating, roll coating, spray coating, and brusk coating are employed.
When the solvent remains in the resulting photo-conductive layer, inconveniences occur frequently, resulting in reduced dark resis-tance, reduced photoconductivity~ or the uns,sitability of photo-conductivityO Hence, it is preferred to perform the drying as completely as possible.
Generally, the photoconductivity is better with smaller thickness of the photoconductive layer, but if it is too low, electrification voltage caused, for example, by corona discharge tends to become lower. Preferably, therefore, the thickness which will give the best image are experimentally determinedO Usually, the thickness of the photoconductive layer 2 to ~0 microns, preferably 4 to 15 microns.
~ he support for forming the photosensitive layer is suitably chosen from metal plates such as aluminum, zinc, copper, nickel or iron, paper sheets, plastic films or glass sheets. When the 6upport is a good electric insulator, the 0~ 6urface to which the photosensitive layer is formed should be~6ubJected to a treatment for rend,-ering it electrically conductlng. Any methods of treatment can be employed so long~as they do not adversely affect the photoconductive sensltive 1ayer and can provide a surface resistivity of 5~not~;more~than 101 ohmg/om2j preferably not more than lO9~ohms/cm~.
As previously stated, the USi3 of the organic ; photoconductors of the present invention for photosensitive layers~is suitable for obtaining transparent or transluent . . ~

'i ;.
.~
~ ~ 38 -. ~ .
~ .
1)` :

.
' : ' ~ , ' - ` ' ' :

109$64Z

electrophotographs, and therefore, plastics films~ paper sheets and glass sheets are frequently used as bases. In many cases, therefore, these bases require treatment to form a transparent conducting layer thereon~ ~or example, this treatment can be performed by a method comprising coating or impregnating a polymeric electrolyte such as poly-N~trimethylbenzyl ammonium chloride or poly(sodium styrenesulfonate) on or in the surface of a base material thereby to form a conducting layer; a method comprising vacuum-depositing a metal such as aluminum, copper, gold or pa~adium in a thin layer on the base surface; a method comprising applying an oxide of indium oxide, for example, to the base surface by vacuum evaporation or spattering, and then increasing its transparency by oxidation, for example; or a method forming a vacuum~deposited layer of copper and converting it to a copper iodide layer using iodidneO 'rhe formation of a conducting layer using an electrolyte is most inexpensive, ahd the transparency of ;~ the layer is good. ~ut since it is ionizing conduction, the resistivity value of the conducting layer varies accord-ing to the degree of moisture absorption. ~he indium oxide laye~r or the copper iodide layer has good transparency and çonductivity, but since they require a complicated procedure for preparation, the cost of production is higho he~ ultrathin metal coating is cheaper than the indium oxide~layer or the copper iodide layer because no post~
treatment is required, but suffers from reduced taran~
sparencyO According to the desired use, a suitable method is chosen.
, ,, , , ~ . . .

' .. .. .~. , . .~ : .
.: ., .. : . . ~. . - - . . -. .

lOg564Z

(v) Characteristics and utility of the electro-photographic sensitive layer ~ he amino-containing photoconductive resin used as a photoconductive base material of the electrophoto-graphic sensitive layer of the present invention can beobtained from a raw material commercially available very easily at low cost by a very simply reaction, and has sensitivity comparable to the conventional low-molecular-weight and polymeric organic conductors. By combining it with a suitable sensitizer and/or binder polymer, there can be obtained electrophotographic sensitive layers having -superior utility according to the requirements of end uses, which have superior flexibility or transparency or superior light transmission in a near ultraviolet region in the preparation of a diazo duplicate as a second master.
Accordingly, the electrophotographic sensitive layer of the present invention can be used in a very wide range of applications. For example, a photosensitive sh~eet for~med by providing the photosensitive layer on a p1astic film can be used as a microfilm, a microfiche or a~second master sheet obtained by directly enlarging a micro-film, ~a~transparent sheet for overhead pro~ectors, or a slide~projectorsO A potosensitive paper prepared by using paper as~a~base can~be used as coated paper copy for bus-25~ ne~ss~offices, ~and a photosensitive paper for a secondmaster.
Furthermore,~when the photosensitlve layer is ormed~on a meta1~plate, an image of a drawing can be formed;thereorl in place of scribing used at the time of , .

` ' . .. . .

~0956~2 metal cutting.
~ 1rthermore, a transfer photosensitive drum for plain paper copying can be produced by forming the photosensitive layer on a metal drum. According to the present invention, electrophotographic sensitive layers having a sensitivity, in terms of a half-decay exposure amount under a white light from a tungsten-filament lamp as a light source, of 2000 to 10 lux-sec can be easily obtained. This sensitivity is fully feasible when good sensitizers are chosen.
~ he following Examples and Comparati~e Examples illustrate the present invention is greater detail.
" .

~ i` . ~ :

.. , . . ~ :- . ~ . . .

.;
.,: i: . . -, . . ~ . . , ~ , ..

10956~2 Before going into the Exal~ples, we shall give a description of t~he materials an~ test methods used in these examples~
tI~ ~Soluble low-molecular-weight polycondensate (1) Xy]ene/formaldehyde resin ~paration A reactor was charged with 106 g of m-xylene, 129 g of a 37o/ agueous solution of formaldehyde (formalin) and 98C~ by weight sulfuric acid, and the reaction was started at 95C with stirringO The reaction was performed for 7 hours, and the temperature finally rose to 104Co After the end of the reaction, the aqueous phase at the bottom (sulfuric acid phase) was separated, and the resul-ting oil phase was steam-distilled at 100C at atmospheric pressure. 107 g of a xylene/formaldehyde resin was obtained.
Characteristics .
Weight-average molecular weight: about 390 Oxygen content- about 8O 7% by weight 2aAcid number: 0O2 ,~ : :
~ ~ Viscosity: 74 centipoises (determined for a toluene `: : solution with a xylene resin concentra-tion of 80% by weight) I Composition of functional ~roups he ~R spectrum of the xylene/formaldehyde resin was measured using deuterochloroform (CDC13) 3S a solvent, and the following peaks were co.nfi.rmedO

,i !~
!

1,~

.

1C1956~2 ( ppm) (1) Ar-CH3 2026 (m) (2) Ar~CH20CH3 3~32 (m) (3) Ar-CH2-Ar 3.84 (s) (4) Ar-CH2(0C_2~nAr ~ , (m) Ar-cH2oH J
(~In (1) to (4), Ar represents an aromatic ring~
(5) Phen~l proton 7 (m) In the peak of (4) above, the peaks of Ar-CH2(0CH2~nAr and Ar-CH20H overlap ~nd are broad~
~hus, Ar-CH20H was acetylated to Ar-CH200CCH3. Measure-ment of its ~MR spec~rum shows that Ar-CH200CClI~ was 1.8 ppm (Ar-CH200CCE3, 4.8 ppm). ~hese peaks were sep~rated from the peak of Ar-C~ (OC_2~nAr', an~ the co~nposition of the ~unctional groups c~lculated for each of the peaks was as follows:

(Moles of each functional ; (o/l~groups~per benzene ring) , .
;Ar-CH2CH 2.20.10 -CH20~H3 ~ 6.7Q.21 ~ ;

Ar-CX2-Ar ~ ~ 4.20.48 Ar-CH2~ CCH ~ Ar 9.;8 ~ C.32 2)~ Hlghly~condensQd xylene/formaldehyde resin Thls resin~was~obtained~b~ further condensing t ~ ~ ~,ne/forma1~ehyde~resin (l)~above.

haraDt~ris~os ~
; Welght-average molecular weight ~ 1300 Acid nurnb~r ~ ; b~low 7 oftenïng point (ring-an~-ball method) 105 - 1~5C.

; - 43 -, ,. ~ .. ~. . . . .. . . . .

-, . . . .

lOgS6~2 Moles of cunctional Functional ~roups group Per benzene ring Ar-CH2-Ar 0~70 Ar-cH2(ccH2~nAr 0.17 (3~ Resol resin This resin was obt~ined by condensing mix~d cresol (m:p=6:4~ and form~ldehyde using sodium hydroxide as a catalyst.
Characteristics Weight-average molecular weight: 270 Viscosity: 0~45 poises Non-volatile content: 55/~ (135Co7 7 hrs.) Specific gravity (25C~: 10020 Composition of the functional groups ~oles of each functional Functional ~ e~ group Per bensene ring Ar-CH2-Ar 0.4 Ar-CEI20EI o.5 Binder (a~ Vinyl acetate resin ~;20~ his resin was obtained by polymer1zing vinyl ; acetate.
ah~r~Çter lstlCS ~ `
; Wei~ght-average molecular weight: 1050 Volat~ile~matter: below 3~J by weight ~25 `~ V1scosity: 1200 centlpoises when determined at 30Co the;resin ~ f ranspar~ncy: 95/~ determined for a 1~/~ methanol solution at 480 m~
.~

l - 44 -,:
,.

.

` ~ . ~ ' - ~ ' ' ~,os~6~Z

Apperent density: 0078 Specific gravity(25C4): 1.20 ~Softening point: 55Co Melting point: 87 to 88C~ :
Melt viscosity (170C.): 1.47 x 103 centipoises (b) Acrylic resin ~his resin was obtained by polymerizing methyl methacrylate, butyl methacrylate and acrylic acid in a weight ratio of 20:778:1.
10 Characteristics Acid number: 3~7 Weight average molecular weight: 2500 Solidscontent: 49~80/.? by weight (c) Polycarbonate resin ~his was a commercially available polycarbonate obtained from bisphenol A (4,4'-dihydroxydiphenyl-2,2-'` propane) and phosgener Characteristics :We1ght-average molecular weight: about 35,000 2~ Specific gravity: 1,4 Oxidation initiation temperature: 300Co e) ~ : 5ster resin his resin was obtained by copolycondensing an aald~component conslst mg of 46 mole% of terephthalic acid 25~ and 54 mol~e% of lscphthalio acld and a glycol component consis.ting of 45 mol~e% of~e-thylene glycol and 55 mole% of neop~ntyl~glyool~

f~` : :. .
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` ~ `

:, . : . , . . : .

~09~6~Z

Characteristics ~eight-average molecular weight: about 1700 Specific gravity: 1O26 Inherent viscosity: 0O5~ when determined at 30C
for a solution of 0O~ g of the ester resin dissolved in 100 mlO
of a mixture of phenol and tetrachloroethane (6:4) Softening point: 1 63 C o (e) Polystyrene resin ~his was a commercially available styrene resin obtained ~y polyn(erizing a styrene monomer, and had a weight average molecul~r weight of about 100,000 and a density of 1.045.

(f) Vinyl chloride copolymer ~his resin was obtained by copolymerizing 91 mole/~ of vinyl chloride, 3 mole,! of vinyl acetate and 6 : mole% of vinyl alcohol.

Characteristics Wei~ht-average degree of polymerization: about 420 ~ . :
Apparent density: 0.65 Volatlle content:~ 3%

Solution viscosity:: 220 centipoises determined for . a 2~' solution of a 1:1 mixture of methyl isobutyl ketone and toluene at 25C.
g~ All~d re~in ~ :
his is;:a~commercially available modified alkyd r~sin;whloh:was prepared by reacting glycerin and coconut ;oil;to form~a mono~lyoeride whlch was then reacted with pht:halic:~anhy~ride. A ~6~/o xylene~solution of this resin s~ had:~a~:specific gravity of 1~02~, an acid number of 3, and

6 -:, . .. : -: - . :, ~ - -lOgSi64Z

a viscosity (Gar-~ner) of V - YO
,upports ~he following m~terials were used as suppor-ts on which to for~l the electrophotographic sensitive layer.
c, (a) ~luminu~ plate An aluminum plate having a thickness of 300 microns whose surface was polished with lO00 mesh emery.
(b~ Tracing paper rendered electrically conducting A sheet of tracing paper for general engineering drawings was immersed in a 10/ aqueous solution of poly-vinylbenzyltrimethyl ammonium chloride, and driedO Both surfaces of the tracing paper thus had a coating of poly-vinylbenzyltrimethyl ammonium chloride at a rate of 2 g/m2O ~his paper will be referred to as "T-Paper"O
(c~ Polyeth~lene terephthalate film rendered electrically conducting A lO0~-thick biaxially oriented polyethylene terephthalate film w~s immersed in a 100/'/! aqueous solution :
of polyvinyltrimethyl ammonium chloride an~ dried. Both 20~ ~surfaces of the film thus had a coating of polyvinyl-benzyltrlmethyl ammonium chloride at a rate of 2 g/m2.
his film will be referred to as "Ph.T film"0 (d) ~ Metal-deposlted film Metallic indium was vacuum-deposited on a 75~-2.~5~ thick~biaxially oriented polyethylene terephthalate film, and~then air oxidized to form a transparent coating. It had a transmittanoe at 480 m~ of 8~ and a surface resis-tivity of about 400 ohms/cm2O

, . :
. ~ ~
.
~ - 47 -: . ' .

' lOg56~2 [IV~ Preparation of s~ecimens t`or measurement of pho-tosensitive characteris-tics The soluble low-molecular~weight polycondensate, the binder and chemical sensitizer shown in each of the h~amples were dissolved in ~he in~licated amounts in each of the solvents shown in the Exa~plesO A 1/~ by weight di-methyl formamide solution of an op-tical sensitiZer was pre-pared, and mixed with the above solution, followed by good stirring~ '~he reslllting solution was coated on a support by means of a Wheeler coater or a wire bar, and dried at 70G for 15 hours to form a sensitive layer having a thick-ness of about 7 microns on the supportu tV~ Method for m~asuring the photosensitive ch~racteri3tics ~ volta~e of -6 KV ~las applied to a ~quare speci-men with one side measuriIlg about 10 cm using a corona dis-charger of the corotron type at a rate of 5 meters/min.
'rhe surface potential of the specimen was then measured by a hi~h level surface potentiometerO '~he high level surface ~potentlometer was connected to a recorder which recorded the potential measured. '~he li~ht source used was a 30W
tungæten-filament lamp unless otherwise indicated. It was fixed ~t a position 49 cm away from the specimen~ '~he illumination intensity of the lamp at that p0sitiOll was 1 25 ~5 lux.
he half-decay, e~poæure was calcul~ted from the ~fo1lowing equation.~

Ialf de(aY 3xposure = ~ x t (luxosec3 1~:
~ 48 -I

' ' ' :

ioss6~z .~n electric charge was a~plied to the specimen by corona discharge in a darkroom7 and it.s potential (Vo) was rea~ after ~ lepse of 35 secondsO At the en~ of this 35-fiecond period, light (with a illumination i.ntensity of ,-L lux~ was irradiated onto the specimen from a tungsten-filament lamp. '~he time (t seconds) until the potential (Vo) reached Vo/2 was readO
~VI~ ~lethod of evaluating print ima~es ~fter measuring the half-decay exposure (E50) in a darkroom, a corona charge of -6 ~V was applied to `:
the entire surface of the specimen at a rate of 5 m/minO ~ .
~he specimen was exposed imagewise using a test chart to the light from a 30W tungsten-filament lamp which had an illumination ~mount 4 times as large as the half-decay exposure. The exposed specimen was developed by liquid . 'development or dry development de~cribe~ below.
;;: (1~ Liquid development ~ he exposed specimen waC, dipped for several 5~ seconds~ln~a dispersion of a toner (particle size Ool to 20:~: l.0 micron). ~he toner dispersion had been prepared by '' B ~ well~ neading a~mixture ;consisting of 15 g of Pentarol ~0 :trademsr'k), 15:g of:a copolymer of lauryl methacrylate and~styrene (mol~r ratio of 95:5; weight average molecular welght~of about lO~,OOO~, 150:g of cab carbon black and 25~ 15~g~xylene~:and~dlspersing the mixture in 3 liters of ., 1so-p~araffin (C9~-:Cl~5)~:using ultrasonic oscillation. ~he . .' Pentarol:;20 lS a~phenol-modified pentaerythritol ester of :~
ros~l~(wlth~an:acid~number:of lO, a specific gravity at 2QO of~1009,;and a melting po mt of l.lO to l~oQoO ~.

~' . : . . : . , , .. , , , ~ ,., :, . , , . :
~: - . . , - . . ~
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~1~956'iZ

(2) Dry ~evelopment (magnetic brush development) 200 Parts by weight of reduced iron powder with a size of 1'~0 to 300 mesh ~Jas mixed with 5 parts by weight of a toner consisting of 1 part by weight of a styrene/butadiene copolymer, 0O0~ part by weight of poly-styrene, Ool part by wei~ht of c~rbon black and 0.18 part by weight of oil black which had been melt mixed, cooled and pulverized to an average particle size of 10 microns.
(~he toner used had a particle size of 5 to 25 micronsO) ~he resulting mixture was adhered to a rod magnet, and contacted frictionally with the exposed specimen to de-velop ito ~he resulting images were evaluated on the following scale.
Excellent: Very clear print images were obtained.
Good: Despite some defects, the print images were substantially satisfactory.
Poor: Much fog occurred, and the images were unclear; or no print image was observed.
~ .
ExamPle l Preparation of a soluble aromatic tertiary amino-20~ contalning re~sln A 100 m~ three-necked flas~ was charged with 17 g of;the xylene/formaldehy~e resin~, 16~7 g (Ool mole) af c~rbazole and 0.17 g~of 2,~4-dimethylbenzenesulfonic acid to~ be~referred to as m-xylenesulfonic acid) as a catalyst, ~25~ a~d~they were reacted~at~200aO in a stream of nitro~en.
The~reaction product~was dlssolved in 50 ml. of toluene at room temperature. ~he solution was added tQ 100Q mlO
of stirred~methanol in a mlxer. ~he~precipitate obtained , ~ .

:
., .. :. -~ . , :
` .
.

~ogs6d~

was separated by filtration, and dried at 70C and 1 mmHg absO for 15 hours to afford 25 g of a pale green white tertiary amino-containing resin which had the fo]lowing characteristics.
Melting point: 135C.
Inherent viscosity: 0~26 N content: 4.16/~ by weight Aromatic amino group content: 0.70 per benzene ring NMR spectrum: A peak (12.3 ppm) base on ~I~H
of carbazole was no at all observed. :
(2) Formation of a photoconductive layer and the measurement of its characteristics 2 g of the tertiary amino-containing resin ob-tained in (1) above was dissolved in 10 mlO of chloro-benzene at 20C to form a solutionO
~5 On the other hand, metallic indium.was vacuum deposited on the surface of a polyethylene terephthalate film having a thickness of 75 microns and an area of` 10 cm2, and then air oxidized to form a transparent conductive ,~
~ film having a resistivity of 400 ohms/cm2O
; ~ !
he solution obtained was coated on the surface of thls f~llm using a Wheeler coater, and dried at 70Co for~l5 hours to form a photosensitive layer having a :thlckness of 7 microns.
he half-decay exposure (~50) of this photo- :
; ~ ~ .
as ~ ~sensitive: layer7 as measured by using light with an illumi- :.
:nation intensity~l0000 lux from a 300-W tungsten-filament lamp, was 1.8 x 104 lux.sec. After a lapse of one month, the coating still adhered to the polyethylene terephthalate 1 - :

, . . . . . . . .
.. .~ ....... . . : .
; : - . . : . . :

109S6~2 film, and no precipitate was seen to occur on the surface, and the photoconductive layer had a transparency of more than 70~o _mparative Example 1 B lo g of polyvinyl carbazole (~,uvican M-170, a product of BASF) was pulverized and dissolved in 100 ml.
of methylene chloride, and re-precipitated with 1000 mlO
of purified methanol, followed by drying. ~his procedure was repeated -thrice to purify the polyvinyl carbazole.
One gram of the purified polyvinyl carbazole was dissolved in 10 ml. of chlorobenzene to form a 10~ solution.
In the same way as in Example 1, the ,solution was coated on the aluminum pla-te to form a coating. ~he half-deca~ exposure (E50~ of this coating, measured in the same way as in Example 1, was 1.6 x 10 luxo sec.
~he resulting coating had many cracks and was susceptible to breakager When the polyvinyl carbazole solution was coated ; on the transparent conducting polyethylene terephthalate ;2Q~ fllm in the same way as in Example 1, the photosensitive coating peeled off, and it was impossible to measure the photosensitlve characteristics of the coating and to èvaluate print images.
E~amPle~s 2- to 18 ~`
25~ 600 mg of the tertiary amino-containing resin obtained in~Example 1,~ , the binder and the chemical sensltizer shown in ~able I were mixed with each of the solvents shown in ~able 1 to form a solution. The solution was mixed with a separately prepared 1/~ by weight dimethyl ~ :

a ~7~

10956~Z

formamide solution of each of the optical sensi~tiæers shown in Table 1 with stirring at room temperatureO ~he mixture was colted on each of the supports shown in ~able 1 us:ing a rotary coater, and dried to form a photosensitive layer having a thickness of 7 micronsO
~ he half-decay exposure (E50) of the photo-sensitive layer and the quality of print images, were determined, and the results are shown in ~able 1.

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Note:
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Br Br CH ~ \ r ~ B ~

(n is 7 on an average~ ~ :

(~2) : .
A copolymer of vinylidene chloride and vinylchloride (l:l) having a weight-average molecular weight of about l00,000 and a melting point of 85Co ExamPle 20 and Comparative ExamP1e 2 A l00 mlO three-necked flask was charged with l0 g of the highly condensed xylene/formaldehyde resin ~.
6~8 g (0.041 mole) of carbazole and 0.l0 g of m-xylene-sulfonic acid, and the reaction was carried out for 4 hours at 200C 1n an atmosphere of nitrogenO The resulting ~ -product was~dissolved in 25 mlO of toluene at room tem-peratUrei and the solution was added to 800 mlO of stirred methanol in a:mixer.~ The preCipitate obtained was separated by~filtrat1on, and dried at 70C and l mmHg absO for 15 hours to afford~9.5 g of a white tertlary amino-containing resin having the following characteriatics~
Me1ting point~ 15C~ :
Inherent visco sity~: 0.12 :
;; N~cont~ent:~ 2~,5C~o:
A peak (l2:.~3 ppm)~based:on t~he: ~ ~H of carbazole ;was not at all obaerved:by an NMR spectrum analysis.
~ ~ .
t ~
57- :

- - ............. . . .. . -: . . . - . . . -- -, . , . . - . . . . .

~09S64Z

~ he photosensitive character~.StiCs of the resul-ting resin were compared with those of a mere mixture of benzyl carbazole of the following formula 6 and the highly condensed xylene/formaldehyde resin ~ (Comparative Example 2) which had the same nitrogen con-;~ tent as the above tertiary amino-containing resin. ~he ;~ : re:sults are shown in Table 2.
,~
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lOgS64~

~abl e 2 -- . .--~
~xample I ~xample 20 Comparative Example 2 ___ _ _ . __ ~
Photoconcluctive Tertiary amin.o- ~lixture of benzyl carbazole resin (mg) containing resin (255) and the highly con-(600) densed xylene/formaldehyde condensate (300) Solvent (ml~) Chlorobenzene (3) Chlorobenzene (3) Binder (mg) Ester resin (100) Ester resin (100) Solvent (mlL) Chlorobenzene (0O5~ Chlorobenzene(0O5) ~ :
. __ . , Chemical Bis-(4-dimethyl- Bis-(4-dimethylaminophenyl) sensitizer (mg) aminophenyl) methane (200) methane (200) Solvent (mlO) Chlorobenzene (1.0) Chlorobenzene (1.0) _ Optical Crystal Violet Crystal Violet sensitizer . _ Support Aluminum plate Aluminum plate Half-decay 330 Not sensitive even when :
exPosure ~E50) the light source was (lux.sec) made five times more bright _ _ _ ___ _ _ . .
5valuation of ~xcellent poor print images _ _ _ _ .~
: . .
~xamples 21 to 31 : In the same manner as in Example 1, (1), the reaction Was carried out at the temperatures and for the times:indicated in Table 3 using the various aromatic amines;shown in ~able 3 instead of the carbazoleO ~he yaeld,~melting point, inherent viscosity, and N content of the resulting tertiary amino-containing resins, were measured,~ snd the~results are shown in ~able 3O
0.6 g of each of the resulting~ tertiary amino-containing resins was dissolved in 3 ml. of methylethyl :- ketoneO Ool g of the ester resin was clissolved in 0.5 ml.
~:~
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' ' ~ ' . '. '' ' ~ . ': ' :

10~S64 ;~

oL ~ethyl ethyl ketone. ~urthermore, 002 g of 2,2'-methylenebis(4-chlorophenol) was dissolved irl 1 ml. of methyl ethyl ketone. Gn the other hand, 0.5 mg of Crystal ~Jiolet was dissolved in 50 ml~ of (limethyl formamide.
'~hese solutions were mixed at room temperature with stirring, and the mixture 1~?~s coated on each o~ the supports shown in '~able 3 using a Wheeler coater, and dried at 70co for 15 hours to form a photosensitive l~yer having a thickness of about 7 microns.
?~he half-decay exposure of each of -the specimens obtained was measured, and the resulting prin-t images were ovaluated. The rssults are sho~ ~n Table 3.

t, C

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lOg56~Z

Table -3- (1) __ Example ~ 21 22L~ 23 ~ 24 25 . -- r- ~ _ ~
Xylene/formal- I !
~eh~de resin 10 20 5 j 10 20 I (~

_ ._____.... , ___.___ ___ __ __ _ ___._ __,_ __ Aromatic Diphenyl- AnilineBenzyl. Methyl a- ::
amine (g) amine (26O7) aniline aniline Naphthyl-(10) (4.4) (]0O28) amine . . _ __ _ _._ _ _ _ ___ (9.2) m-Xylene __ - - - ~ ~
sulfonic acid On 1 0.2 0.05 0.1 0.2 :
(g) __ ~__ _ ~: ' Reaction temp~rature 200 200 200 200 200 ( C n ) Reaction 2 time ~hrs O ) 2 _ _ ___ _.__ _ __ _____ _ _ :
Yield (g) 10.7 24 _____ _ 10 li~i Melt~c 6~i - 70 I28 30 65 59 - 61 ; Inheren~ 0.09 0.13 0.08 0.10 0.07 . .
. _ _ __ ~: conte~t (%) 3.75 4.29 3.75 4.69 2060 - -- ~ : ~ _ _ ~,.... ..
Support ~1 ~ T-paper A]. Al Al ~alf-decay : ~
~exposure: 228 ~390 293 293 780 ùx.sec~ ~
_ Ev~aluation :
D~ the~ ~Excellenb Excellent Excellerlt T3xcellent Excellent : -:~ : L.

(*)~: ~:When only: the~; xylen~/formaldehyde resin was used, thls value was 3.5 x I0 (as determined b~ the same method as in;Example l)u i:~ ~,, ~ ~ , .. : . . .. . . .
,, ,:, :

~O~S~42 ~able -3- (2) __ __,__._ _ _. ___ _._ I Example ¦26 1 27 i 28 29 30 I ~ _ I --t - ~_ _ ~_ .
Xylene/formal-dehyde resin 10 lO 10 20 20 (~) .. _ __.__ __ ~_ . _____ _ Aromatic Indol N,N'-Di- Pheno- N,N'-Di- o_ amine (g) (7Or~) phenyl-p- thiazine amino- . I~oluidine phenylene- (1208) diphenyl- ¦ (6085) diamine methane I (12.5) (501) Carbazole . (1701) _ _ m-Xylene sulfonic Ool O~l Ool 0.2 002 acid (g) Reaction temperature 200 200 200 200 200 Reaction 2 2 2 2 2 time (hrsO ) .... ___ Yield (g~ ~ _._~ 3 12.9 1',.6 36 18~5 pOelinitn~Oc ) 74 80 - 82 lO0 73 - 75 96 - 98 .............. __ _ .. .
scos ty 0.08 0.07 0.10 0007 0 lO
~ Nitrogen 5.13 5.58 4.26 5O03 3.68 :: _ ~ __ : ~upport Al Al A1 A1 Al :Half-decay exposure . 1120 1900* 97 1200 975 ux. ~c _ __ ___ _ ~Evaluation of ~the print Excellent Good Excellent Excellent Excellent mages l .

: : * Bis-(4-dimethylami~.ophenyl)methane was used as a chemical ~: sensitizer.

.
' :
: . .
` ~' -. . -:

lO~S6~2 Com~arative ExamE~e 3 ~ xample 22 was repeated using a mere mixture of dibenzyl aniline of the formula ~ z~r~>

and the highly condensed xylene/formaldehyde resin which had the same nitrogen content insteacl of the tertiary amino-containing resin used in Example 22. The photosensitive characteristics of the resulting coated layer were meàsured, but it did not show any sensitivity. When a tungsten-filament lamp having an illumination intensity five timesas great as that used above was employed, t~e layer did not shGw any sensitivity, either.

i ! E~amPle ~1 500 mg of the tertiary amino-cc)ntaining resin formed between the xylene/formaldehyde resin and diphenyl-amine shown in Example 21 and 500 mg of the tertiary amino-containing resin formed between the xylene/formaldehyde re~sin and~ N~N',diphenyl-p-phenylenediamine shown in Example 27~were each dissolved in 6 mlO of methylethyl ketone con-` 2Q~ t~ain~ng lOO mg o~ trinitrofluorenone. Each of the resultingsolut~ions~was coated on the~aluminum plate using a Wheeler coflter,~;~a~d~dried.~ he half-decay exposure measured was 350~1ux.~sec and 600~1ux.sec, respectively~ ~he print images were excellent m both casesO
25~ xamPlqs 32 to ~7 hese Examples use various cocondensation com-ponents.

! I
~` - 63 --1: . ~

'~ ~ ' ' ~ ' ' ' : : .
, lO~S6~Z

~ he xylene/formaldehyAe resin, c~omatic amino compound, cocondensation component and catalyst (m-xylene-sul.fonic acid) were re~cted in the proportions shown in ~able 4 at the temperature and for the time shown in Table 4. ~he yield, melting point, inherent viscosity and nitrogen content of the resulting terti.ary amino-containing resins were measured, and the results are shown in ~able 4.
Using each of the resins obtained, electrophoto-graphic sensitive layers were prepared in the same manner as in Example 1 (non-sensitized), and the half-decay exposure and the quality of print images were determinedO
On the other hand, using each of the resins obtained, electrophotographic sensitive layers were prepared : in accordance with the recipe of Example 19 (in the case f Examples 32 to 35) and the recipe of Example 10 (in the case of Examples 36 and 37), and the half-decay exposure and the quality of print images were determined.
he results are both shown in Table 4, :: : - 64 -i ~ ~

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xamples 38 to 55 ~ he tertiary amino-containing resin obtained in Example ~2 (a concondensate of the xylene/formaldehyde resin, carbazole and anthracene) was mixed with each of the binders, chemical sensitizers and optical sensitizers shown in Table 5 in the proportions indicated in ~able 5 ~he resulting mixture was coated on each o.f the supports shown in ~able 5, and driedO ~he photosensitive charac-teristics of the resultirg photosensitive layers were measured, and the results are shown in ~able 50 .

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_x~ le 56 500 mg of -the tertiary amino-containing resin used in Exar.~ple 35 (the cocon~enxate prepared from the ~Jlerle/formaldehyde resin, carbazole, anthracene and t-butylphenol), and 100 ~g of 2,4,7-trinitrofluorenone were dissolved in 6 ml of methyl ethyl ke-toneO ~he resulting solution was coated on the aluminum plate using a rotary coater, and driedO The half-decay exposure amount of the resulting photosen.sitive l.ayer was 95 luxo sec. ~he print image was of excellent qualityO
Examples 57_and 58 10 g of the same tertiary amino-containing resin obtained in Example 1, (1) was dissolved in 50 mlO of chloroform, and the solution was contacted with a solution of 80 ml of chloroform in 8 g of bromine to brominate the resin. Thus, 8O6 g of a mo~ified tertiary amino-contain-ing resin having the followin~ characteristic5 was obtainedO
Melting point: 175 ~ 178Co Inherent viscosity: 0009 Bromine content: 28~84% by weight ~itrogen content: 2089,'~by weight Proportion of aromatic amino groups per benzene nucleus: 0~78 ~he resulting tertiary amino-containing resin was mixed with the binder resin, chemical sensitizer and optical sensitizer shown in Table 6 to form a coating solution. ~he coating solution was coated on the aluminum plate, and dried~ The half-decay exposure of the resulting photosensitive layers and the quality of the print images _ 71 -~0956~Z

were determined. and the results are shown in r~able 60 Table 6 r~
Example 5~ 59 _ __ __ __ _____ ~ertiarv ~lino-con-taining resin (mg) 600 ~,00 Solvent (ml) I Methylethyl Chlorobenzene ketone (300) (3.) _. _ _ ~
Binder (mg~ Ester resin Ester resin (100) (100) Solvent (ml) ¦ Methylethyl Chlorobenzene ketone (0.5) (005) Chemical bis-(4-dimethyl- 4-chloro-3-nitro-sensitizer (mg) aminophenyl)benzoic acid m~thane (200) (200) Solvent (ml) MethylethylChlorobenzene ketone (1.0) (1.0) _ Optical Crystal VioletCrystal Violet sensitizer (mg) (05) (005) Half-decay exposure 98 410 .
P _g Excellent Excellent ~xample 59 500 mg of the brominated tertiary amino-containing resin used in Example 58, 300 mg of 2,4,7-trinitrofluorenone, and 50 mg of Crystal Violet were dissolved in 10 ml. of methyl ethyl ketoneO The resulting solution was coated on the aluminum plate using a Wheeler coater, and driedO ~he half-decay exposure of the resulting photosensitive layer was 14 lux.s~c which means very high sensitivity~ The quality of the resulting print image was excellent.

.

.:
.

, ' ' ~

iO9~6~Z

Ex~ple 60 A lOO ml three-necked flask was charged with 2305 g (non-volatile sontent 52,b~ of the resol resin, 16.7 g of carbazole and 002 g of m-xylenesulfonic acid, ~nd they were stirred at 80C for l hour in an atmosphere of nitrogen to distill off the volatile component contained in the resol resinO ~he reaction was continued fcr an additional 2 hours at 230C to afford 22 g of a black brown tertiary amino-contflining resinO ~easurement of the NMR spectrum of the product showed no peak (1203 ppm) ascribable to ` N_ of the carbazoleO It was thus con-firmed that all the starting carbazole reacted with the resol resinO
The tertiary amino-containing resin obtained had the followin~ characteristics.
Melting point: above 300 CO
Inherent viscosity: 0~274 Nitrogen content: 5.79% by weight Aromatic amino content per benzene nucleus: 1~41 ~he resulting product was dissolved in N-methyl-pyrrolidone to form a 10% solutionO ~he solution was coated on the aluminum plate by a Wheeler coater, and dr1ed by a vacuum dryer (l mmHg absO) at 70C for 12 hours.
The half-decay exposure amount of the resulting photo_ ~25 sentitive layer, measured using a 100-W tungsten-fil~ment lamp of 300 lux, was 7~00 luxOsecO

' -'' lOgS642 Com~arative Exa~ 4 1007 g (OolO mole) of N-monomethyl aniline, 7D5 g (0~10 mole) of 37% formaldehy~e (formalin) and 12 ml of cone. hydrochloric acid were placed in a 100 mlO three-necked flask, and reacted at 100C for 8 hoursO ~hereaction product was neutralized to a pH of 7 using a sodium carbonate solutionO The solid was filtered, washed with water, and dried at 50C and 1 mmHg for 12 hours to afford 1008 g (mOpO 85 - 86C) of a blaek solid. From the faet that the nitrogen eontent of the produet determined by elemental analysis was 11063% by weight, it was presumed to be a 1:1 (mole) condensate between N-monomethyl aniline and formalin.
Coating was attempted in the same way as in Example 20 using the resulting eondensation produet. But it had poor solubility in eommon solvents, and a uniform eoating eould not be obtainedO

. . .

- .- .. - . -- -: ' . ' . . . . . :

': ' ': '. : ,,

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An electrophotographic sensitive layer which comprises:
(1) at least one solvent-soluble aromatic amino-containing photocon-ductive resin as a photoconductive base;
(2) at least one sensitizer selected from the group consisting of optical sensitizers and chemical sensitizers; and (3) at least one solvent-soluble binder polymer having compatibility with said solvent-soluble aromatic amino-containing photoconductive resin (1) said solvent-soluble aromatic amino-containing photoconductive resin (1) being a reaction product of (i) a soluble low-molecular-weight polycondensate comprising a xylene/formaldehyde resin or a resol-type phenolic resin with (ii) an aromatic amino compound of the formula (2) wherein Ar is an aromatic group, the group is bonded to the carbon atoms of the aromatic ring, n is 1 or 2, and Y is a hydrocarbon residue which optionally forms a ring with Ar either directly or through a nitrogen, oxygen or sulfur arom; and when n is 1, Y may be a hydrogen atom; said poly-condensate having a molecular weight of 200 to 3,000 and having dimethylol ether groups, methylol groups and/or functional groups thereof, the content of said groups being one per 0.1 to 3 benzene rings of said polycondensate, said reaction product containing, bonded to the benzene ring, as pendant groups, at least one N-methylene aromatic amino group of the formula (4) wherein Ar is an aromatic group, the group is bonded to the nuclear carbon atom of the aromatic group, n is 1 or 2, and Y is a hydrocarbon residue or a hydrogen atom and optionally forms a ring together with Ar either directly or through a nitrogen, oxygen or sulfur atom, or is optionally bonded to the benzene ring through a methylene group at a rate of at least one per 0.5 to 7 benzene rings, said N-methylene aromatic amino group being selected from the following group:
and

2. The electrophotographic sensitive layer of claim 1 wherein said soluble aromatic tertiary amino-containing resin has an inherent viscosity, determined at 30°C for a solution of this resin dissolved in N-methyl-pyrrolidone in a concentration of 0.5 gram/100 ml., of 0.03 to 0.8.

3. The electrophotographic sensitive layer of claim 1 wherein said benzene-type compound is m-xylene.

4. The electrophotographic sensitive layer of claim 1 wherein said aromatic amine compound is expressed by the following formula (2') wherein Ar is an aromatic group containing a benzene or naphthalene nucleus containing 6 to 15 carbon atoms; said benzene or naphthalene nucleus optionally contains 1 to 3 substituents selected from the group consisting of alkyl groups containing 1 to 3 carbon atoms, alkoxy groups containing 1 to 3 carbon atoms, aryloxy groups containing 6 to 10 carbon atoms, N,N-di-lower alkyl-substituted amino groups and halogen atoms; n is 1 or 2; and Y is an aliphatic hydrocarbon residue containing 1 to 10 carbon atoms or an aromatic group having the same definition as Ar, and may contain the same substituents as mentioned above with regard to Ar, and when n is 1 Y may be a hydrogen atom, and Y and Ar optionally form a ring by being bonded to each other either directly or through a nitrogen, oxygen or sulfur atom.

5. The electrophotographic sensitive layer of claim 1 or 4 wherein said aromatic amine compound is selected from the group consisting of aniline, toluidine, N-methyl-aniline, N-ethylaniline, N-benzylaniline, carbazole, and diphenylamine.

6. The electrophotographic sensitive layer of claim 1 wherein the aromatic portion of the aromatic amino compound contains at least 3 aromatic rings selected from the group containing of anthracene, perylene and phenanthrene, and the resol type phenolic resin is selected from the group consisting of phenol, o-cresol, m-cresol, p-cresol, mixed cresol, 3,5-xylenol and t-butylphenol.

7. The electrophotographic sensitive layer of claim 1 or 6 wherein said chemical sensitizer has the properties of an electron acceptor, or is a halogen-containing organic compound.

8. The electrophotographic sensitive layer from claims 1, 4 or 6 wherein said chemical sensitizer is a halogenated phenol or its derivative.

9. The electrophotographic sensitive layer from claims 1, 4 or 6 wherein said optical sensitizer is a triarylmethane type dye compound.

10. The electrophotographic sensitive layer from claims 1, 4 or 6 wherein said soluble aromatic amino-containing resin contains an aromatic tertiary amino group derived from carbazole or its nucleus-substituted de-rivative, and has blended therewith at least one chemical sensitizer of the following formula (5) wherein R1 to R4 are identical or different, and represent an alkyl, alicyclic or aralkyl group containing 1 to 7 carbon atoms, and R5 represents at least one of a hydrogen atom and alkyl, alicyclic, aryl and aralkyl groups containing 1 to 7 carbon atoms, and are identical or different and represent a lower r alkyl group containing 1 to 3 carbon atoms or a halogen group, and p and p' represent an integer of 0 to 2.

11. A soluble aromatic tertiary amino-containig photoconductive resin, which is a reaction product of (1) soluble low-molecular-weight polycondensate which is an addition-condensation reaction product of (a) a benzene compound containing at least one nitrogen-free electron donating nucleus substituent and at least two nuclearly substituted hydrogen atoms capable of methylol substitution with (b) formaldehyde or its functional derivative, and in which at least one of the residues of said benzene compound contains a substituent of the following formula wherein X is a hydroxyl group, an alkoxy group, an O-acyl group or a halogen atom, bonded in principle to the carbon atoms of the benzene ring as a pendant group, with (2) an aromatic amine compound of the following formula wherein Ar is an aromatic group, the group is bonded to the carbon atom of the aroma-tic ring, n is 1 or 2, and Y is an aromatic group which is identical to or different from Ar, and optionally forms a ring together with Ar either directly or through a nitrogen, oxygen or sulfur atom; the hydrogen atom bonded to the nitrogen atom forming the amino group of the aromatic amine being substituted by the methylene group bonded to the carbon atoms of the benzene ring.

12. A process for preparing an electrophotographic material, which comprises coating on a support a solution in an organic solvent of said sol-uble aromatic tertiary amino-containing photoconductive resin and at least one of said chemical sensitizers and/or optical sensitizers, and said binder polymer; and drying the coating to remove the organic solvent substantially.

13. An electrophotographic sensitive layer which comprises: (1) at least one solvent-soluble aromatic amino-containing photoconductive resin as a photoconductive base; (2) at least one sensitizer selected from the group consisting of optical sensitizers and chemical sensitizers; and (3) at least one solvent-soluble binder polymer having compatibility with said solvent-soluble aromatic amino-containing photoconductive resin (1); said solvent-soluble aromatic amino-containing photoconductive resin (1) having a molec-ular weight of 200 to 3,000 and comprising a benzene compound of the follow-ing formula wherein ?,?, q and r are positive integers; m is 0 to 4;
(? + q x r) is 1, 2, 3, or 4; ? is a positive integer of 0 to 4; q is 0 or 1, and when q is 0, represents a hydrogen atom: r is 0 or 1, and when r is 0, the benzene ring C is directly bonded to the carbon atom of the benzene ring B; and A and A' are identical or different and represent at least one member selected from the group consisting of alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, a hydroxyl group and halogen atom; and when ? or ? is 2 or more, A
and A' may be different members selected from the above group, and at least one of A and A' should be an electron donating group selected from the above group, said benzene rings B or C being substantially bonded through a methy-lene group, and said resin containing bonded to its benzene rings, as a pen-dant group, at least one N-methylene aromatic amino group at a rate of at least one per 0.5 to 7 benzene rings, said N-methylene aromatic amino group being selected from the following group:
and