DE4306047A1 - Colour electrophotographic material esp. for making colour proof - with photoconducting layer contg. ordered copolymer, polymer with polar and cyclic anhydride gps. and curable polymer for good image transfer - Google Patents

Abstract

Electrophotographic material for colour printing can be used in the prodn. of colour proofs by electrophotographic prodn. of colour toner image(s) on a transfer sheet and transfer to a sheet material. The material has a base (I), photoconducting layer (II) and transfer layer (III) in this sequence. (II) consists of a polymer (P), at least near the interface with (III), a polymer (Q) and a polymer (R), which has unit(s) with photocurable and/or thermosetting gp(s).; and the surface of (II) in contact with (III) has an adhesive strength not more than 150 p (JIS K 0237/1980). The polymers are: (P1): a linear block copolymer with a segment contg. at least 50 (wt.)% units contg. F and/or Si atom(s) and a segment (Y) contg. a unit with photocurable and/or thermosetting gp(s).; (P2): a star-shaped copolymer with at least 3 block copolymer chains of type AB, consisting of X and Y blocks, joined by an organic gp. (Z); (P3): a graft copolymer with X segment(s) and Y segment(s); (P4): a block copolymer of type AB or ABA contg. X segment(s) and Y segment(s), including graft segment(s) X' and/or Y' with Mw = 1 x 10 3 to 2 x 10 4; X' contains macromonomer segment(s) (MA) with at least 50% units with F and/or Si atom(s); and Y' contains macromonomer segment(s) (MB) with no units contg. F and/or Si atom(s); (Q1): a homopolymer or random copolymer with Mw = 1 x 10 3 to 2 x 10 4, contg. at least 30% units of the formula -CH(a1)-C(a2)(COOR3)- (IV), polar -PO3H2, -SO3H, -COOH, -PO(OH)(R1) and/or -OR2 gp(s). (V) and cyclic anhydride gps. (VI); a1 and a2 = H, halogen, CN or hydrocarbyl; R1-3 = hydrocarbyl; (Q2): a linear block copolymer with Mw = 1 x 10 3 to 2 x 10 4, contg. segment(s) (M) with at least 30% (IV) units and segment(s) (N) contg. (V) and (VI). USE/ADVANTAGE - For the prodn. of colour proofs (claimed). Control proofs can be produced easily and constantly without colour shift and with excellent precision and image quality, whilst the material can be produced easily and economically and has stable electrophotographic properties. Good, clear, stable prints are obtd., even under unfavourable conditions, e.g. relatively high or low temp. or atmos. humidity, and these have excellent electrostatic properties, even when scanned with semiconductor laser beams.

Description

The present invention relates to an electrophotograph nice material for the color examination, especially a verb in the photoconductive layer of the electrophotograph chemical material for the color test or for the colorant In the following, occasionally as photosensitive Material will be designated.

Photosensitive plates are due to their excellent Quality, print durability, dimensional stability and ver Dirt resistance mainly for multi-color printing been used. Photosensitive plates (PS plates) are prepared by applying a photosensitive layer, the a diazo resin or an o-quinone diazide as a main component contains, on an aluminum substrate, its surface behan for the purpose of improving its hydrophilic properties delt was produced. These PS plates are replaced by a Color-separated and halftone film exposed to UV rays and to remove the photosensitive layer in the non-photosensitive layer Image areas designed to be the surface of the hydrophilic To expose aluminum plate, thereby obtaining printing plates become. A multi-color image can be obtained by clicking for each color a printing plate by the above method was produced, mounted on a printing press and using inks that are each of these colors correspond to a print on a sheet of printing paper gear.

After confirming that a series of editing, Plate making and printing processes, such as B. Input from Character, layout, color determination, etc. as determined be performed, and that it is between the color again etc., which is received, and those received by one Client is desired, no difference will be necessary corrections are made and then a regular printing done. This level is called "Press correction". The former is called as  referred to as "first proof" and is performed to each to check the above-mentioned method in a printing works fen. The latter is called "second proof" and is carried out to be approved by the client receive. The second proof is almost in the same way as a proof for the regular printing carried out, including Lich the types of printing inks and Druckpa to be used pier. The resulting trigger has almost the same quality as a deduction of printed material by a regular Printing process was received. That by using regulä rem printing paper used in regular printing is to be carried out proof-printing is called "regular cor rectification ".

The color determination and the sound reproduction of a color photograph phie should be confirmed and corrected individually for each color become. In particular, the pressure for the client in general repeated several times. So far the proof-printing using a color-separated and halftone films used in regular printing supposed, and a PS plate that is relatively inexpensive and of poor print durability is, for. B. with the press-on press, whose mechanism is similar to that of the press under the Name "the flatbed four-color proof-press" is known manufactured by Dainippon Screen Co., Ltd. Service. The above-mentioned method is called "press proof" called and is not comfortable, since it is time consuming, ge trained staff required for operation and the Beibehal making constant quality difficult.

There are some suggested methods for color proofing who do not use the press-on press that has a a press-like mechanism, and therefore easier to carry out and lead to a stable pressure These are due to their advantages, such. B. simple operation and stability after repeated use preferably used. It will be "proof outside the press"  named and typical species and systems of which are in Bulletin of the Printing Society of Japan 24, No.3, page 32 (1989) described. Examples of the systems include systems that under the trade name "Color Art" by Fuji Photo Film Co., Ltd., "Cromalin" from Dupont and "Matchprint" from 3M are available. These systems use a color sepa movie, but do not use the above mentioned printing press.

The color-separated film is generally used made a color scanner. The scanner reads data from Original and performs a color separation, formation of Halbtö and a sound playback control to digital data to deliver. A silver halide film is made with laser beams, which are modulated by the digital data, scan-be clears, develops, fixes and dried to a positi Ven or negative color-separated film for multicolor to get pressure.

More recently, an electronic plate making is system called "full color scanner" ent wrapped and used. The system performs Ver go through to retouching or record collection by and therefore it requires a first proof, with which one the resulting quality can be faster than that systems in use so far. If the result rende properties such. B. a kind, a layout, the Quality of color separation for some patterns and the tone reproduction, using a press correction method as it is up is in use, judged, the efficiency decreases of the system, since it compared to the proofs of the Prior art from the issued product to the color separated film and the production of a press proof or a proof outside the press takes a long time.

Because the image data is accessible as digital information in the system There are some systems with direct digital color  printing that does not use the pressure previously used, been proposed. Details can be found in "Printing Infor mation, April, page 2ff (1991) such systems include a silver halide system electrostatic toner system (a wet electrophotograph nice system), an inkjet system and a thermal Sublimation transfer system.

Among these systems is the wet-electrophotographic System in terms of precision, image quality and sound-re It is particularly excellent and is beneficial to everyone Paper type can be used for the system, so that a Correction on regular paper can be done since charged in the system, a photoconductive element, the Laser beam exposed and each with a color toner, the a pigment each having one of four colors, d. H. cyan, magenta, yellow and black, in an electrically insulating Liquid comprises, is developed and then the resul transmitting toner image is transferred.

However, it is quite difficult to get a toner image from the top surface of the photosensitive plate directly to regular To transfer paper. JP-A-2-272469 describes a Tech nik, which solves these problems but involves several steps.

It has been suggested on the surface of the light sensitive element a removable transfer layer to provide a toner image on the transfer layer generate and picture together with the transfer layer on regular paper (see JP-A-61-174557 (corresponding to JP-B-2-43185), 1-112264, 1-281464 and 3-11347). Among them, only that described in JP-A-61-174557 is described System used in practice. However, in this system will the photoconductive layer through a transparent Layer support (a polyethylene terephthalate) exposed and therefore this system requires that also the photoconductive layer is transparent. In addition, the  This system is not reusable and therefore very expensive.

JP-A-1-112264 and 1-281464 describe an image forming apparatus method of color printing method which uses a light sensitive paper that is a photosensitive element comprises, on the in the order given a removable Layer and an adhesive layer are arranged, used and which is characterized in that a toner image developed kelt and with the removable layer on regular paper is transmitted.

However, it is difficult to obtain such a photosensitive Layer evenly in a usable size in practice It is also difficult to produce a toner image without Transfer damage.

The same applies to the method described in JP-A-3-11347 which uses a recording medium at a removable topcoat on a photoconductive Layer is applied.

In addition to the problem of diminished picture quality due a poor transfer of the toner image as above It is also desired, the problem of diminished Image quality due to defects during the electro photographic formation of the toner image, in particular due to the reduction of electrostatic properties, occur to solve.

There were the properties of electrophotographic mate materials comprising a known photoconductive layer, under different environmental conditions at the picture manufacturer (eg higher or lower temperature or higher or lower temperature) lower humidity) and it was gefun that the electrophotographic properties of the mate materials (in particular, the charge retention in the dark and the photosensitivity) deteriorates in some cases  and the materials were not stable and good pictures could deliver.

When electrophotographic materials for color proofing, which are used with a direct digital system can, by the scanning exposure method using Semiconductor laser beams are illuminated, they have to be better electrophotographic properties, such as. B. electrostatic properties (in particular charge retention in Dun and photosensitivity), as compared with a conventional fully simultaneous exposure such a system using visible light Method requires longer exposure times and the exposure intensity of the same is limited.

When the above-mentioned known electrophotographic Materials that, as is known, in such systems used, the diminished Quality of the resulting pictures. In particular, they showed up in the resulting images dirt of the back Basically, fine lines disappeared and characters became smeared.

An object of the present invention is the provision an electrophotographic material for color proofing, with which the above-mentioned problems are solved.

Another object of the present invention is the ready a control print without color shift and with Excellent precision and picture quality, light and easy can be obtained consistently.

Another object of the present invention is the ready position of a photoconductive layer that is light and co can be produced inexpensively and stable electrophoto has graphical properties.  

A still further object of the present invention is the Providing a method for producing a color proof using a toner image with the help of a the transmission device can be easily transmitted and a control deduction on any type of transmission paper can be produced.

A still further object of the present invention is the Providing an electrophotographic material for Color control prints, which can provide clear and good pictures, even if the imaging in an unusual environment exercise, such as B. at higher or lower temperature or higher or lower humidity is performed.

Finally, an object of the present invention is the Providing an electrophotographic material for Color control prints, which regardless of the type of sen sensitizing dyes used in the photoconductive Layer to be used, a Farbandruck with more stable and excellent picture quality can deliver and which out drew electrostatic properties, even when scanning using semiconductor laser beams is exposed.

The above problems are solved by using an electrophotographic material for color proof comprising, in the following order, a support, a photoconductive layer and a transfer layer, which can be used for producing a color control print in a process in which at least one color toner image is produced electrophotographically on the transfer layer and then transferred together with the transfer layer to a sheet material to provide the color control print herzu, wherein the photoconductive layer from the fol lowing polymers (P ₁ ), (P ₂ ), (P ₃ ) and (P ₄ ) selected polymer (P); a polymer selected from polymers (Q ₁ ) and (Q ₂ ) (Q); and a polymer (R) containing at least one unit with one or more light and / or thermosetting groups,
wherein the polymer (P) is present at least in the region near the surface opposite to the transfer layer, and
the surface of the photoconductive layer in contact with the transfer layer has an adhesive strength of not more than 150 p (gram · force) as measured by the pressure-sensitive tape and sheet test of JIS Z0237-1980;
Polymer (P ₁ ):
a linear block copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one polymer segment (Y) containing units with one or more light-curing and / or thermosetting groups ent, comprises;
Polymer (P ₂ ):
a star-shaped copolymer containing at least three AB-type block copolymer chains containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s) and at least one polymer segment (Y) comprising units having one or more photocuring and / or thermosetting groups, said block copolymer chains being linked together by an organic group (Z);
Polymer (P ₃ ):
a graft copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one polymer segment (Y) containing units having one or more light-curing and / or thermosetting groups comprises;
Polymer (P ₄ ):
an AB or ABA type block copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one polymer segment (Y ) comprising units having one or more light-curing and / or thermosetting groups, wherein at least one of the polymer segments (X) is the following graft-type polymer segment (X '), at least one of the polymer segments (Y) is the following polymer segment (Y ') is of the graft type, or at least one of the polymer segments (X) is the following graft-type polymer segment (X') and at least one of the polymer segments (Y) is the following graft-type polymer segment (Y ') :
(X '):
a polymer segment having a weight average molecular weight of from 1 × 10³ to 2 × 10⁴ and containing at least one macro-monomeric segment (M _A ) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s) contains;
(Y '):
a polymeric segment having a weight average Molekularge Klobuk of 1 × 10 ³ to 2 × 10 ⁴ which contains at least one macro monomer segment (M _B), which does not contain units having fluorine atom (s) and / or silicon atom (s);
Polymer (Q ₁ ):
a homopolymer or random copolymer having a weight average molecular weight of from 1 × 10 ³ to 2 × 10 ⁴ and containing not less than 30% by weight of units represented by the following formula (I):

-CH (a ₁ ) -C (a ₂ ) (COOR ₃ ) - (I)

wherein a ₁ and a ₂ each independently represent hydrogen, halogen, cyano or a hydrocarbon group, R _{3 represents} a hydrocarbon group;
and at least one polar group selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, -PO (OH) (R ₁ ), wherein R _{1 is} a hydrocarbon group or -OR ₂ (R ₂ = Hydrocarbon group), and residues of cyclic anhydrides;
Polymer (Q ₂ ):
a linear block copolymer having a weight-average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing at least one segment (M) containing not less than 30% by weight of units of the above formula (I), and at least one Segment (N) having at least one polar group selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, -PO (OH) (R ₁ ), wherein R _{1 represents} a hydrocarbon group or -OR ₂ (R ₂ = hydrocarbon group), and residues of cyclic anhydrides.

A photoconductive layer according to the invention can be any Layer in which a photoconductive compound in one Binder or a binder resin is dispersed. With other words, a single-layer type consisting of only one single layer, or a multilayer type (or Function-separated type), which is a charge-generating A layer comprising a photoconductive compound dispersed therein contains therein dispersed, and a charge transport be used. In the present inventions It is of the utmost importance that the polymer (P) in the Area near the surface, that of the transfer layer is opposite, distributed, and that the surface of a has improved removability.

In the photoconductive layer in which the functions ge can be separated, the charge transport layer, with the Transfer layer is in contact, the polymer (P) and contain the polymer (R), and the charge generation layer The photoconductive compound and the polymer (Q) ent hold. Alternatively, in the photoconductive layer with separate functions the charge transport layer, which with the transfer layer is in contact, the polymer (P), the polymer (Q), the polymer (R) and the photoconductive Connection included.

The polymer (P) is preferably in the layer containing the Transfer layer touched, in an amount of 1 to 30 wt .-%, based on the total weight of the layer containing.  

The polymer (Q) is preferably in the layer containing the contains photoconductive compound, in an amount of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, per 100 Parts by weight of the photoconductive compound included.

The polymer (R) is preferably in the layer containing the Transfer layer touched, in an amount of 5 to 99.1 Wt .-%, based on the total weight of the layer containing.

Binder or binder resin is used in the present Description of the invention as a resin defining a Ma trix in which a photoconductive compound dis is polymerized, the polymer (P), the polymer (Q), and the poly mer (R) and other resins, if necessary in the photo conductive layer may be present.

Preferably, the photoconductive layer of the present the invention, a light-curing and / or thermosetting Medium. The light-curing and / or thermosetting agent is in the description of the present invention as a verbin Defined, oligomer or polymer, the (that) by light and / or heat and / or a crosslinking agent can.

The present invention further relates to a method for forming a color control print in which at least one Color toner image electrophotographically on the electrophotograph chemical material for the Farbandruck, which angege in the angege order a substrate, a photoconductive layer Layer and a transfer layer comprises, formed and then together with the transfer layer on a sheetmate rial to produce the color control print.

The attached drawing shows the following.

Fig. 1 schematically shows a heat transfer apparatus used in the present invention.

Reference numeral 1 denotes a metal roller coated with a rubber; 2 denotes a built-in heater; 3 denotes a device for measuring the surface temperature; 4 denotes a temperature control device.

The presence of the polymer (P) in the area near the Surface opposite to the transfer layer ver lends the photoconductive layer such detachability, that the transfer layer is slightly different from the photoconductive one Layer can be detached.

When the solution for forming the photoconductive layer, the the polymers (P), (Q) and (R), on the support is applied, the polymer (P) migrates to the upper upper surface of the layer and condenses there to the surface To give detachability. Further, the polymer is (P) orien by pointing segment (X) to the transfer layer and the segment (Y) in the interior of the photoconductive Layer shows, since the segment (Y) has a high compatibility having the polymer (R). Thus, the segment (X) gives the surface removability. Segment (Y) holds together work with the polymer (R) the polymer (P) near the top surface. In other words, with the polymer (P) and the Polymer (R) achieved an anchor effect.

In addition, since the polymer (R) and the segment (Y) of the Polymers (P) light-curing and / or thermosetting groups and preferably the photoconductive layer contains light-curing and / or thermosetting agents, both the polymer (P) and the polymer (R) by light or Heat cured and the above orientation of the polymer (P) can be fixed.

As a result, when the transfer layer on the pho  Tungsten layer is applied, the migration of the Polymer (P) hinders the transfer layer to the Interface between the transfer layer and the photo to keep the conductive layer clear.

Accordingly, when the electrophotographs of the present invention material for the color proof for producing a color Control print is used, an electrophotographic formed multi-color toner image along with the transfer Layer transferred to a sheet material to the color Kon troll withdrawal.

Next, depending on the nature of the transfer layer used thermoplastic resins a Lö for the application of a transfer layer is used to be selected. Because some solvents however, with binders for the photoconductive layer have high solvating ability, they affect the dispersion of the polymer (P) in the photoconductive Layer, resulting in deterioration of the electrophotography phical properties, such. B. Pollution of the hind and deterioration of image quality.

The above problem is solved by crosslinking binders in the photoconductive layer of the present invention to give it solvent resistance.

Since the photoconductive compound-containing layer contains the Polymer (Q) contains as a binder, the photoconductive Ge compound in the layer evenly dispersed and be dispersed. Further, even if the photoconductive this compound is sensitized by a sensitizing dye sensitized, the polymer (Q) regardless of the Type of sensitizing dye sufficient with the pho interacting with the conductive compound. Insbeson In the system according to the invention, the latter can be the photoconductive Compound also sufficiently with a sensitizing color  material for semiconductor laser beams interact, while using the dye in electrophotographic Materials that are conventional binder resins treat can not interact.

Although the present invention is not limited by any Theories, it seems that the above Effect is achieved by the fact that the polymer (Q) on the surface of the particles of the photoconductive compound is adsorbed without the interaction between the sensitizing dye and the photoconductive Ver Binding disturbs, and it the dye coating on the Oberflä surface of the photoconductive compound particles in good State holds. As a result, it seems that the electrophoto graphic properties are kept good and stable can, even if the ambient conditions become noticeable change, for. By using a higher or lower one Temperature or a higher or lower humidity.

When the photoconductive layer is of the single-layer type, are a photoconductive compound, the polymer (Q), the Polymer (R) and a small amount of the polymer (P) together present in one shift. In such multi-component layers, the polymer (Q) can also sufficiently with the photoconductive compound interact without passing through the Polymer (R) to be disturbed, whereby the layer out were awarded electrostatic properties. The polymer (P) may also be added to the upper surface of the layer migrate to this surface of the layer an excellent To give detachability.

The removability of the photoconductive layer of the present The invention was by means of the adhesive strength, by the pressure-sensitive tape and sheet test of JIS Z0237- Measured in 1980. The adhesive strength must not more than 150 p (g · f), preferably not more than 100 p, In particular, not more than 50 p to get a good replacement  availability of the photoconductive layer.

The above pressure sensitive tape and sheet test is under Use of the electrophotographic according to the invention Material for color proofing, but without transfer layer, performed as a test plate, being a pressure sensitive Band with a width of 6 mm is used and with a Peel speed of 120 mm per minute is measured. The adhesive strength is calculated by measuring the measured Value in the value that with a band of 10 mm width he is enough, converted.

The adhesive strength of the surface of the photoconductive Layer after the transfer layer has been formed and stripped off is that of the photoconductive surface Layer before the formation of the transfer layer equivalent.

The support, the photoconductive layer and the over tragungsschicht the electrophotographic invention Materials for color proofing will now be described in detail wrote.

layer support

Layer support may be a known support. virtue wise, the substrate is photoconductive. examples for photoconductive supports include: a metal, Paper or plastic-made substrate that handles was to give it conductivity, z. B. by impregnation nierung with a material with low insulation resistance; a substrate whose backside (i.e., the side which is the te, on which the photoconductive layer is applied, opposite) conductivity is conferred and on the at least one coating was applied, for. B. to it prevent, to wave; a substrate on its surface a waterproof adhesive layer was applied; the the latter substrate, wherein optionally at least a precoat layer was applied; and a substrate,  a laminate on paper of a plastic sheet with Leitfä ability is what a material, such. As aluminum, steam-abge was divorced.

Examples of conductive substrates or a layer carrier, which imparted conductivity as described above have been described in the following publications: Yukio Sakamoto, "Electrophotographics" 14, (No.1), pages 2 to 11, (1975); Hiroyuki Moriga, "Chemistry of Special Papers", Poly mer Publishers (1975); M. F. Hoover, J. Macromol. Sci. Chem. A-4 (6), 1327-1417 (1970).

Photoconductive layer The polymer (P)

The polymer (P) is selected from the polymers (P ₁ ), (P ₂ ), P ₃ ) and (P ₄ ). All of these polymers are block copolymers comprising segment (X) and segment (Y).

Preferably, the segment (X) contains not less than 80 Wt .-%, in particular not less than 90 wt .-%, based on the total weight of the segment (X), units with fluorine atom (s) and / or silicon atom (s). Preferably contains Segment (Y) 1 to 60% by weight, in particular 5 to 40% by weight, based on the total weight of the segment (Y), units with one or more photocurable and / or thermosetting Groups.

The weight ratio of segment (X) to segment (Y) in Polymer (P) is preferably 5:95 to 95: 5, especially 10: 90 to 90: 10.

The fluorine atoms and / or silicon atoms having unit may preferably have at least three fluorine atoms, if it contains no silicon atoms. It preferably contains at least two silicon atoms, if they ent no fluorine ent holds. Further, it may be at least one fluorine atom and one silicene  contain ziumatom, if they are both fluorine and silicon contains atoms.

The polymer (P ₁ )

The polymer (P ₁ ) is a linear block copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one Polymer segment (Y) containing units with one or more light-curing and / or thermosetting groups.

The polymer (P ₁ ) may be any type of linear block copolymer, such as. B. a block copolymer of type AB (such as (X) - (Y)) or a polymer having multiple blocks A and B or a block copolymer of the type ABA (such as (X)) (Y) - (X) or (Y) - (X) - (Y)).

The weight-average molecular weight of the polymer (P ₁ ) is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ⁴ to 5 × 10 ⁵ . The weight-average molecular weight of the segment (X) in the polymer (P ₁ ) is preferably not less than 1 × 10 ³ .

The polymer (P ₂ )

The polymer (P ₂ ) is a star-shaped copolymer comprising at least three block copolymer AB-type chains consisting of at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and or silicon atom (s), and containing at least one polymer segment (Y) containing units with one or more light-curing and / or thermosetting groups, these block-copolymer chains being bonded together via an organic group (Z) are.

These segments (X) and (Y) may be present in any order in the AB block polymer chains of the star copolymer (P ₂ ). For example, the polymer (P ₂ ) may have the following formulas:

(Z is an organic group (Z), (X) represents the segment (X) and (Y) represent the segment (Y)).

The organic group (Z) should preferably no longer as 15, especially not more than 10 block copolymer chains be bound by the type AB.

The weight-average molecular weight of the polymer (P ₂ ) is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ⁴ to 5 × 10 ⁵ . The weight-average molecular weight of the segment (X) in polymer (P ₂ ) is preferably not less than 1 × 10 ³ .

The organic group (Z) can be any kind of molecule a molecular weight of preferably not more than 1000 his. Examples of organic groups (Z) include carbon Hydrogen groups with a bond of not less than three on, z. For example, the following groups:

(r ¹ to r ⁶ each independently represent a single bond, a hydrogen atom or a hydrocarbon group, with the proviso that at least one group of groups r ¹ and r ² and at least one of groups r ³ to r ^{6 is} a single bond or represents a group with a valence of not less than two).

These hydrocarbon groups may be present either alone or in combination. In the latter case, the organic group (Z) can further one or more connec tion groups, such as. For example, -O-, -S-, -N (r ⁷ ) -, -COO-, -CON (r ⁷ ) -, -SO ₂ -, -SO ₂ N (r ⁷ ) - (r ⁷ each independently a hydrogen atom or a hydrocarbon group), -NHCOO-, NHCONH- and a radical of a heterocyclic group having one or more heteroatoms, such as. Oxygen, sulfur and nitrogen (such as thiophene, pyridine, pyran, imidazole, benzimidazole, furan, piperidine, pyrazine, pyrrole, piperazine).

Examples of connection groups further include one Combination of the above-mentioned linking groups and one Group one coming from the groups with the following formulas is selected. However, the organic group (Z) is not limited to those set forth here.

The polymer (P ₃ )

The polymer (P ₃ ) is a graft copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s) and at least one polymer segment (Y ) comprising units with one or more light-curing and / or thermosetting groups.

The weight-average molecular weight of the polymer (P ₃ ) is preferably 5 × 10 ³ to 1 × 10 ⁶ , particularly 1 × 10 ⁴ to 5 × 10 ⁵ . The weight-average molecular weight of the segment (X) in the polymer (P ₃ ) is preferably not less than 1 × 10 ³ .

The segments (X) and (Y) may be present in any order in the polymer (P ₃ ). That is, the polymer (P ₃ ) may, for. B. have the following formulas:

The polymer (P ₄ )

The polymer (P ₄ ) is a block copolymer of the type AB or ABA containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one polymer segment (Y) containing units having one or more thermosetting and / or light-curing groups, wherein at least one of the polymer segments (X) is the following graft-type polymer segment (X '), at least one of the polymer segments ( Y) is the following polymer segment (Y ') of the graft type, or at least one of the polymer segments (X) is the following poly mersegment (X') of the graft type and at least one of the polymer segments (Y) the following polymer segment (Y ' ) of the graft type is:
The graft-type polymer segment (X '): a polymer segment having a weight-average molecular weight of from 1 × 10 ³ to 2 × 10 ⁴ and comprising at least one macromonomer segment (M _A ) containing not less than 50% by weight. %, preferably not less than 90% by weight, of units containing fluorine atom (s) and / or silicon atom (s).

Comprises a polymer segment that has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and at least one macromonomer segment (M _B) which has no units having fluorine atom (s): The polymer segment (Y ') graft type and / or silicon atom (s).

The segments (X) and (Y) may be present in the block copolymer (P ₄ ) in any order. That is, the polymer (P ₄ ) may, for. B. have the following formulas:

The segment (X) may contain the macromonomer segment (M _A ) z. B. in an amount of 1 to 50 wt .-%, preferably 3 to 30 wt .-%, based on the total weight of the segment (X) included.

Segment (Y) may contain the macromonomer segment (M _B ) e.g. B. in an amount of 1 to 50 wt .-%, preferably 3 to 30 wt .-%, based on the total weight of the segment (Y) included.

Preferably, the macromonomer segment (M _B ) contains the units with light-curing and / or thermosetting groups in an amount of 1 to 50 wt .-%, preferably 3 to 20 wt .-%, based on the total weight of the macromonomer segment ( M _B ).

The weight-average molecular weight of the polymer (P ₄ ) may be e.g. B. 5 × 10 ³ to 1 × 10 ⁶ , preferably 1 × 10 ⁴ to 5 × 10 ⁵ , amount. The weight-average molecular weight of the segment (X) in the polymer (P ₄ ) is preferably not less than 1 × 10 ³ .

In the following, the segments (X) and (Y) will be described in detail wrote.  

The units with fluorine atom (s) and / or silicon atom (s) may have one or more substituents with fluorine atom (s) and / or silicon atom (s).

The substituent (s) may be in a main chain of the polymer (P) or in a side chain thereof his.

Examples of the substituent with fluorine atom (s) include: -C _h F _{2h + 1} (h = an integer of 1 to 18), - (CF ₂ ) _j CF ₂ H (j = an integer of 1 to 17 ), -CFH ₂ , monovalent organic groups having the following formulas:

-CF ₂ , -CFH and divalent organic groups having the following formulas:

Examples of silicon atom (s) groups include tige and divalent organic groups with the following Formulas:

-Si (R ₁ ) (R ₂ ) (R ₃ ) and -Si (R ₄ ) (R ₅ ) -.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, each representing: an optionally substituted hydrocarbon group having 1 to 22 carbon atoms, an organic group having fluorine atom (s), -OR as mentioned above '(R' represents a hydrocarbon group of 1 to 22 carbon atoms which may be substituted) or -OSi (R ₁ ') (R ₂ ') (R ₃ ') (R ₁ ', R ₂ 'and R ₃ ' have each independently the same meanings as R ₁ to R ₅ ). Examples of R ₁ to R ₅ , R 'and R ₁ ' to R ₃ 'include an optionally substituted alkyl group having 1 to 18 carbon atoms, such as. Methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 2-cyanoethyl, 3,3,3-trifluoropropyl, 2- Methoxy ethyl, 3-bromopropyl, 2-methoxycarbonylethyl, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl, an optionally substituted alkene ylgruppe having 4 to 22 carbon atoms, such as. 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, 4-methyl-2-hexenyl, an optionally substituted aralkyl group with 7 to 12 Koh atoms, such as. Benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl, dimethoxybenzyl, an optionally substituted alicyclic cal group having 5 to 8 carbon atoms, such as. As cyclohex yl, 2-cyclohexylethyl, 2-cyclopentylethyl, a given case if substituted aromatic group having 6 to 12 carbon atoms, such as. Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxy phenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chloro phenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonyl, phenyl, acetamidophenyl, propioamidophenyl and Dodexyloyl amidophenyl.

The substituent with fluorine atom (s) and the substituent with Silicon atom (s) can be used either directly or via a Ver be connected to each other.  

Examples of the linking group include bivalent groups, such as. B. -O-, -S-, -NR ₁ -, -SO-, SO ₂ , -COO-, -OCO-, -CONHCO-, -NHCONH-, -CONR ₁ -, -SO ₂ NR ₁ -, a divalent aliphatic or aromatic group, or a combination of these divalent groups. R ₁ has the same meaning as stated above.

Examples of divalent aliphatic groups include:

(e ₁ and e ₂ each independently represent a hydrogen atom, a halogen atom (for example a chlorine atom or a bromine atom) or an alkyl group having 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, chloromethyl, Bromomethyl, butyl, hexyl, octyl, nonyl and decyl, and Q is -O-, -S- or -NR ₂₀ -, wherein R _{20 is} an alkyl group having 1 to 4 carbon atoms, -CH ₂ Cl or -CH ₂ Br stands).

Examples of divalent aromatic groups include: a benzene or naphthalene radical and a heterocyclic radical Group of 5 or 6 members (at least one heteroatom out the group containing oxygen, sulfur and nitrogen). These aromatic groups may, for. B. by a halogen atom (such as fluorine, chlorine or bromine), an alkyl group with 1 to 8 carbon atoms (such as methyl, ethyl, propyl, butyl,  Hexyl, octyl), an alkoxy group of 1 to 6 carbon atoms substituted (such as methoxy, ethoxy, propoxy, butoxy) his.

Examples of heterocyclic groups include furan, thio phen, pyridine, pyrazine, piperazine, tetrahydrofuran, pyrrole, Tetrahydropyran and 1,3-oxazoline.

The following groups (a-1) to (a-33) are examples of Units with fluorine atom (s) and / or silicon atom (s). you However, they are for illustrative purposes only and do not constitute any Limitation of the present invention.

In these examples, -R _f stands for the following substituents:

1) -C _n F _{2n + 1} ,
2) -CH ₂ C _n F _{2n + 1} ,
3) -CH ₂ CH ₂ C _n F _{2n + 1} ,
4) -CH ₂ (CF ₂ ) _m CFHCF ₃ ,
5) -CH ₂ CH ₂ (CF ₂ ) _m CFHCF ₃ ,
6) -CH ₂ CH ₂ (CF ₂ ) _m CFHCF ₂ H,
7) -CH ₂ (CF ₂ ) _m CFHCF ₃ ,
8) -CH (CF ₃ ) ₂ ,

(R _f 'also has the meanings given above under 1) to 8).)
In the above and following formulas, n is an integer of 1 to 18, m is an integer of 1 to 18, l is an integer of 1 to 5, and b is a hydrogen atom or a methyl group.

R ₁ 'R ₂ ' and R ₃ '= alkyl groups having 1 to 12 carbon atoms.

The macromonomer segment (M _A ) preferably has a weight average molecular weight of from 1 × 10 ³ to 2 × 10 ⁴ . A weight-average molecular weight of less than 1 × 10 ³ results in too short grafting portions, resulting in poor removability of the photoconductive layer. A weight average molecular weight of more than 2 × 10 ⁴ leads to lower reactivity with monomers corresponding to other units, which means that the desired graft copolymer can not be obtained.

The macromonomer segment (M _A) can be one that corresponds to a macromonomer which the above-mentioned units having fluorine atom (s) and / or silicon atom (s) that have been specified for the segment (X) which may contain. There may be included a polymerizable double bond group represented by the following formula (II) in one end of the main chain thereof.

CH (a ₁ ) = C (a ₂ ) -V ₁ - (II)

in which a ₁ and a _{2 are} each independently a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group or a hydrocarbon group, and V _{1 is} -COO-, -OCO-, (CH ₂ ) _m OCO-, - (CH ₂ ) _m COO- (m = an integer from 1 to 3), -O-, -SO ₂ , -CO-, -CON (T ¹ ) -, -SO ₂ N (T ¹ ) -, -CONHCOO-, - CONHCONH- or -C ₆ H ₄ -, wherein T ^{1 represents} a hydrogen atom or a hydrocarbon group.

Examples of a hydrocarbon group T ¹ include an optionally substituted alkyl group having 1 to 18 carbon atoms, such as. Methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl and 3-bromopropyl, a optionally substituted alkenyl group having 4 to 18 carbon atoms, such as. 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl and 4-methyl-2-hexenyl, optionally substituted aralkyl group having 7 to 12 carbon atoms, such as. B. benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxy benzyl, dimethylbenzyl, dimethoxybenzyl, an optionally substituted alicyclic group having 5 to 8 carbon atoms, such as. B. cyclohexyl, 2-cyclohexylethyl and 2-cyclo pentylethyl, an optionally substituted aromatic group having 6 to 12 carbon atoms, such as. Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbo nylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamino, and phenyl Dodecyloylamidophenyl.

When V _{1 is} -C ₆ H ₄ -, the benzene ring may also carry substituents. The substituents may be selected from halogen atoms (such as chlorine and bromine), alkyl groups (such as methyl, ethyl, propyl, butyl, chloromethyl and methoxy methyl) and alkoxy groups (such as methoxy, ethoxy, etc.). Propoxy and butoxy).

Preferably a ₁ and a _{2 are} each independently hydrogen, halogen (such as chlorine and bromine), trifluoromethyl, cyano, alkyl of 1 to 4 carbon atoms (such as methyl, ethyl, propyl and butyl) , -COOZ ³ or -Z ⁴ -COOZ ³ , wherein Z ^{3 is} a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 Kohlenstoffato men, an aralkyl group having 7 to 18 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, which groups may be substituted by the same groups given as examples of the groups T ¹ , and Z ^{4 is} a hydrocarbon group.

Preferably, Z ^{4 is} methylene, ethylene or propylene.

In particular, in formula (II) V _{1 can be} -COO-, -OCO-, -CH ₂ OCO-, -CH ₂ COO-, -O-, -CONH- or -C ₆ H ₄ - and a ₁ and a ₂ , the same or different, may be hydrogen, a hydrocarbon group having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl and hexyl). Even before one of a ₁ and a _{2 can be} hydrogen.

The polymerizable double bond-containing group of the formula (II) may be bonded either directly or through a linking group to the end of the macromonomer. The Ver linking group may be a divalent organic group, such as. B. -O-, -S-, -Nd ₁ -, -SO-, -SO ₂ , -COO-, -OCO-, -CONHCO-, -NHCONH-, -CONd ₂ -, -SO ₂ Nd ₃ - and -Si (d ₄ ) (d ₅ ) -, a divalent aliphatic or aromatic group, or a combination of these divalent groups. d ₁ , d ₂ , d ₃ , d ₄ and d ₅ each independently represent the same groups given as meanings for T ¹ in formula (II).

Examples of divalent aliphatic groups include: -C (k ₁ ) (k ₂ ) -, -C (k ₁ ) = C (k ₂ ) -, -C≡C-, -C ₆ H ₁₀ - and

(k ₁ and k ₂ are each independently hydrogen, halogen (such as fluoro, chloro and bromo) or an alkyl group of 1 to 12 carbon atoms (such as methyl, ethyl, propyl, chloromethyl, bromomethyl , Butyl, hexyl, octyl, nonyl and decyl)).

Examples of divalent aromatic groups include: Remains of benzene or naphthalene and heterocyclic groups with 5 or 6 ring members (which is at least one heteroatom, the is selected from oxygen, sulfur and nitrogen, ent hold). These aromatic groups may, for. B. by Halo genatome (such as fluorine, chlorine and bromine), alkyl groups with 1 to 8 carbon atoms (such as, for example, methyl, ethyl, propyl, Butyl, hexyl and octyl) and alkoxy groups having 1 to 6 Koh lenstoffatomen (such as methoxy, ethoxy, propoxy and Bu toxy) be substituted.

Examples of heterocyclic groups include furan, thio phen, pyridine, pyrazine, piperazine, tetrahydrofuran, pyrrole, Tetrahydropyran, 1,3-oxazoline, pyrrolidine, piperidine or groups represented by the following formulas:

(wherein Q is -O-, -S- or -NR ₂₀ - (R ₂₀ = alkyl group of 1 to 4 carbon atoms, -CH ₂ Cl or -CH ₂ Br)).

Examples of units created by tying different organic residues on units with one or more Grup with polymerizable double bond, represented by the formula (II) are formed by the following groups:

wherein P _{1 is} -H, -CH ₃ , -CH ₂ COOCH ₃ , -Cl, -Br or -CN, P _{2 is} -H or -CH ₃ , X is -Cl or -Br, n is an integer of 2 to 12 and m is an integer of 1 to 4.

Segment (Y)

The following are the units with light-curing and / or or thermosetting group in segment (Y).

A photocuring and / or thermosetting group is one Group that generates a heat and / or light initiated hair caused reaction of the polymer.

Examples of the photocuring group may be functional Be groups in known photosensitive polymers be used, such. B. those in the following Publications are described: Hideo Inui, Gentaro Nagamat see, "Photosensitive Polymer", published by Kodansha, 1977; Takahiro Tsunoda, "New Photosensitive Polymer", Ver Department of the Printing Society of Japan, 1981; G.E. Green and B.P. Strak, J. Macro. Sci. Reas. Macro. Chem., C21 (2), 187-273 (1981-82); C. G. Rattey, "Photopolymerization of Surface Coatings ", A. Wiley Interscience Publishers, 1982.

Examples of the thermosetting group can be functional Groups in polymers described in the following publications Tsuyoshi Endo, "Densifying of Ther mosetting polymer ", C.M.C. Co., Ltd., 1986; Yuji Harazaki, "The Latest Binder Techniques Handbook," Chapter II-I, Sogo gÿutu Center, 1985; Takayuki Otsu, "Synthesis, Design and New Use of Acrylic Resin ", publication division of Chubukeieikaihatsu Center, 1985; Eizo Omori, "Functional Acrylic Resins ", Technosystem, 1985.

Examples of such groups include -COOH, -PO ₃ H ₂ , -SO ₂ H, -OH, -SH, -NH ₂ , -NHR ₁₀₃ (R ₁₀₃ = hydrocarbon group preferably having 1 to 8 carbon atoms, such as e.g. Methyl, ethyl, propyl, butyl, hexyl, octyl, 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl), radicals of cyclic acid anhydrides, -CONHCH ₂ OR ₁₀₄ (R ₁₀₄ = hydrogen atom or the above-mentioned alkyl group), -N = C = O, groups of the following formulas:

(Z 'is an atomic group required to form a heterocyclic ring together with the nitrogen atom and the ring is a protecting group for -N = C = O), silane coupling groups, titanate coupling groups, -Cd ₉ = CHd ₁₀ (d ₉ and d ₁₀ are each independently hydrogen, halo such as chlorine and bromine, or an alkyl group of 1 to 4 carbon atoms such as methyl and ethyl).

Examples of polymerizable double bond groups include CH ₂ = CH-, CH ₂ = CH-CH ₂ -, CH ₂ = CHCOO-, CH ₂ = C (CH ₃ ) -COO-, CH ₃ -CH = COO-, CH ₂ = CH-CONH-, CH ₂ = C (CH ₃ ) -CONH-, CH ₃ -CH = CH-CONH-, CH ₂ = CH-O-CO-, CH ₂ = C (CH ₃ ) -OCO- , CH ₂ = CH-CH ₂ -OCO-, CH ₂ = CH-NHCO-, CH ₂ = CH-CH ₂ -NHCO-, CH ₂ -CH-SO ₂ -, CH ₂ = CH-CO-, CH ₂ = CH-O-, CH ₂ = CH-S-, and groups having the following formulas

In the following, the macromonomer segment (M _B ) is tert erläu closer.

The weight-average molecular weight of the macromonomer corresponding to the macromonomer segment (M _B ) is preferably in the range of 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ . A weight average molecular weight of less than 1 × 10 ³ leads to an insufficient anchoring effect. A weight average molecular weight greater than 2 × 10 ⁴ leads to poor reactivity for copolymerization of the macromonomer with other monomers corresponding to the other units constituting the segment (Y).

The units constituting the macromonomer segment (M _B ) may be any units containing no fluorine or silicon atoms. Preferably, the macromonomer segment (M _B ) contains from 1 to 50% by weight of units containing one or more light-curing and / or thermosetting groups, based on the total weight of the macromonomer segment (M _B ), examples of the light-curing and / or thermosetting Groups may be the same as those given above for the corresponding groups in the segment (Y) other than the polymerizable double bond groups.

Other units in segments (X) and (Y) in polymer (P) The present invention may be any units which correspond to the monomers which react with the monomers correspond to the above units, are copolymerizable. Examples thereof include units of addition polymers, Polyesters, polyethers and polyimines.

The units of the addition polymer may be those of units be selected from the following formula (III).

- (CH (b ₁ ) -C (V ₂ -R ₁₁ ) (b ₂ )) - (III)

In formula (III), V _{2 has the} same meaning as V ₁ in formula (I), b ₁ and b ₂ have the same meaning as given above for a ₁ and a ₂ in formula (II) and R ₁₁ has the same meaning as T ₁ in formula (II).

The unit of the formula (III) is present in the segment (X ₁ ) in an amount of not more than 50% by weight, preferably not more than 20% by weight. Even more preferably, it is not included therein at all.

The unit of the formula (III) is contained in the segment (M _A ) in an amount of not more than 50% by weight, preferably not more than 20% by weight. Even more preferably, it is not included therein.

The unit of the formula (III) is in the segment (Y) in one Amount of from 0 to 95% by weight, preferably from 5 to 90% by weight, based on the total weight of the segment (Y).

The units of the formula (III) are contained in the segment (M _B ) in an amount of 40 to 100% by weight, preferably 50 to 95% by weight.

Examples of other units that come with the unit of the formula (III) may include units which correspond to monomers having the unit of Formula (III) corresponding monomers are copolymerizable, such as B. units, the acrylonitrile, methacrylonitrile and Vinyl heterocyclic compounds, such as. B. vinylpyridine Vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, Vinyl dioxane and vinyloxaziridine correspond. These others Units are in an amount of less than 20 parts by weight based on 100 parts by weight of the polymer (P) included.

Further, in the segment (Y) of the polymer (P), a unit having at least one polar group selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, -PO (OH) R ¹⁰¹ (R ¹⁰¹ = hydrocarbon group or - OR ¹⁰² , wherein R ^{102 is} a hydrocarbon group) and res th of cyclic anhydrides, in an amount of less than 10 wt .-%, based on the total weight of the segment (Y), be contained.

Preferably, R ¹⁰¹ and R ^{102 are} each independently of one another for an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, such as. Methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl, 2-methoxybutyl, benzyl, phenyl, propenyl, methoxymethyl, ethoxymethyl and 2-ethoxyethyl.

Further, a radical of a cyclic anhydride may be a radical an aliphatic dicarboxylic acid anhydride or an aroma be dicarboxylic anhydride.

Examples of aliphatic dicarboxylic acid anhydrides include Succinic anhydride, glutaconic anhydride, maleic anhydride hydride, cyclopentane-1,2-dicarboxylic anhydride, cyclohexene 1,2-dicarboxylic anhydride and 2,3-bicyclo [2.2.2] octane dicarboxylic anhydride. These cyclic anhydrides can z. By a halogen atom (such as chlorine and bromine) and a Alkyl group, such as. Methyl, ethyl, butyl and hexyl, sub be stituiert.

Further, examples of aromatic dicarboxylic acid anhydrides Phthalic anhydride, naphthalenedicarboxylic anhydride, pyri dicarboxylic anhydride and thiophenedicarboxylic anhydride. These cyclic anhydrides may, for. By a halogen atom, such as For example, chlorine and bromine, and an alkyl group such. Me ethyl, propyl and butyl, hydroxy, cyano, nitro and Alkoxycarbonyl, such as. Methoxycarbonyl and ethoxycarbonyl, be substituted.

The above-mentioned units may be any units be the vinyl compounds with one or more polar Correspond groups, the z. B. copolymeri with a monomer  which corresponds to the unit of the formula (II) ent speaks. The vinyl compounds are z. As described in poly Society of Japan, "Polymer Data Handbook (Fundamentals)", published by Baifukan (1986). Examples of Vinylver compounds include acrylic acids, α- and / or β-substituents Acrylic acid (such as α-acetoxyacrylic acid, α-Acetoxyme ethylacrylic acid, α- (2-amino) ethylacrylic acid, α-chloroacrylic acid re, α-bromoacrylic acid, α-fluoroacrylic acid, α-tributylsilyl acrylic acid, α-cyanoacrylic acid, β-chloroacrylic acid, β-bromo acrylic acid, α-chloro-β-methoxy- and α, β-dichloroacrylic acid), Methacrylic acid, itaconic acid, half ester of itaconic acid, Hal bamides of itaconic acid, crotonic acid, 2-alkenylcarboxylic acids (such as 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid), maleic acid, Half esters of maleic acid, hemiamides of maleic acid, vinyl benzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, Vinylphosphonic acid, vinyl or allyl half-ester of dicarbon acids and esters and amides of these carboxylic acids and sulfonic acid which contain one or more polar groups as substituents contain.

Preparation of the polymer (P)

The polymer (P) or the monofunctional macromonomer corresponding to the macromonomer segments (M _A ) or (M _B ) can be prepared by known polymerization methods as described, for example, in US Pat. As described in the following publications: WJ Burlan, AS Hoffman, "Block and Graft Polymer" (1986, Renhald); RJ Ceresa, "Block and Graft Polymers" (1962, Butterworths); DC Allport, WH James, "Block Copolymers" (1972, Applied Sci.); A. Noshay, JF McGrath, "Block Copolymers" (1977, Academic Press); G. Huvtrez, DJ Wilson, G. Riess, NATO ASI Sev. Sev. E. 1985, 149; V. Percea, Applied Polymer Sci. 185, 95 (1985).

Ionic polymerization reactions in which alkyllithium, Lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium  siumhalogenide, alkylaluminum halides, etc. as Polymerisa tion initiators are used, for. B. in the following Publications described: T.E. Hogeu-Esch, J. Smid, "Recent Advances in Anionic Polymerization" (1987, Elsevier New York); Yoshio Okamoto, Polymer 38, 912 (1989); Mitsuo Sawamoto, Polymer 38, 1018 (1989); Tadashi Narita, polymer 37, 252 (1988); B.C. Anderson et al., Macromolecules 14, 1601 (1981); S. Aoshima, T. Higashimura, Macromolecules 22, 1009 (1989); etc.

Ionic polymerization reactions with an iodine water substance / iodine system, etc. are described in Macromol. Chem., Macromol. Symp. 13/14, 457 (1988); Toshinobu Higashimura, Mitsuo Sawamoto, Papers for Polymer 46, 189 (1989).

Group transfer polymerization reactions are described in D.Y. Sogah et al., Macromolecules 20, 1473 (1987); O.W. Webster, D.Y. Sogah, Polymer 36, 808 (1987); M. T. Reetg et al., Angew. Chem. Int. Ed. Engl. 25, 9108 (1986); JP-A-63- 97609; etc.

Furthermore, living polymerization reactions with porphyrin are Metal complexes described in T. Yasuda, T. Aida, S. Inoue, Macromolecules, 17, 2217 (1984); M. Kuroki, T. Aida, S. Inoue, J. Am. Chem. Soc. 109, 4737 (1987); M. Kuroki et al. Macromolecules 21, 3115 (1988); M. Kuroki, I. Inoue, Organic Synthesis 47, 1017 (1989); etc.

Ring-opening polymerizations of cyclic compounds are in the following publications: S. Kobay ashi, T. Saegusa, "Ring Opening Polymerization" (1984, Ap Plied Science Publishers Co., Ltd.); W. Seeliger et al. Angew. Chem. Int. Ed. Engl. 5, 875 (1966); S. Kobayashi et al., Poly. Bull. 13, 447 (1985); Y. Chujo et al., Macromol cules 22, 1074 (1989); etc.

Next are living photopolymerization reactions in which  Dithiocarbamate compounds or xanthate compounds as In itiator described in the following articles ben: Takayuki Otsu, Polymer 37, 248 (1988); Shunichi Hinoemo ri, Takaiti Otsu, Polym. Rep. Jap. 37, 3508 (1988); JP-A- 64-111 and 64-26619; M. Niwa, Macromolecules 189, 2187 (1988); etc.

Process for the preparation of block copolymers by radica chemical polymerization, wherein a polymer having azo groups or Peroxide groups are used as initiator are in the following publications: Akira Ueda et al., Papers for Polymer 33, 931 (1976); Akira Ueda, Reports by Osaka City Industrial Laboratory 84 (1989); O. Nuyken et al. Macromol. Chem. Rapid. Commun. 9, 671 (1988); Yasuo Moriya et al., Reinforced Plastics 29, 907 (19); Ryohei Oda, Science and Industry 61, 43 (1987); etc.

Process for the preparation of block copolymers from graft Type are described in addition to the above references ben in: Fumio Ide, "Graft Polymerization and Application thereof "(1977, Polymer Publishers); Polymer Society of Yes pan, "Polymer Alloy" (1981, Tokyo Kagaku Doujin); etc.

These methods include, for. For example, a method of grafting of polymer chains by a mechanochemical reaction with Polymerization initiator, chemically active beam (such as Radiation and electron beams) and mechanical application, a method for grafting polymer chains with funktionel len groups on other polymer chains by chemical bonding (Reaction between polymers) and a method for grafting by polymerization of macromonomers.

Process for grafting polymer chains by the reaction between polymers be in the following references be written: T. Shiota et al., J. Appl. Polym. Sci. 13, 2447 (1969); W.H. Buck Rubber Chemistry and Technology 50, 109 (1976); Tsuyoshi Endo, Tsutomu Yokozawa, Journal of Japan  Adhesive Society (Nihonsechakukokaishi) 24, 323 (1988); Tsuyoshi Endo, ibid. 25, 409 (1989); etc.

Process for grafting by polymerization of macromonomes Ren are described in the following references: P. Dreyfuss, R.P. Quirk, Encycl. Polym. Sci. Closely. 7, 551 (1987); P.F. Rempp, E. Franta, Adv. Polym. Sci. 58, 1 (1984); V. Percec, Appl. Poly. Sci. 285, 95 (1984); R. Asami, M. Takari, Macromol. Chem. Suppl. 12, 163 (1985); R. Rempp et al., Ma cromol. Chem. Suppl. 8, 3 (1984); Yushi Kawakami, Chemical Industry 38, 56 (1987); Yuya Yamashita, Polymer 31, 988 (1982); Shiro Kobayashi, Polymer 30, 625 (1981); Toshinobu Higashimura, Journal of Japan Adhesive Society 18, 536 (1982); Koichi Ito, Polymer Processing 35, 262 (1986); Shiro Toki, Takashi Tsuda, Functional Materials 1987, no. 10, 5; Yuya Yamashita, "Chemistry and Industry of Macromonomer" (1989, I.P.C. Co., Ltd.); Tsuyoshi Endo, "Design of Construc tion for Novel Functional Polymer ", Chapter 4 (1991, CMC Co., Ltd.); Y. Yamashita et al., Polym. Bull. 5, 361 (1981); etc.

Process for the preparation of star block copolymers are described in the following references: M.T. Reetz, Angew. Chem. Int. Ed. Engl. 27, 1373 (1988); M. Szwarc, "Carbanions, Living Polymers and Electron Transfer Processes "(1968, Wiley, New York); B. Gordon et al., Polym. Bull. 11, 349 (1984); R. B. Bates et al., J. Org. Chem. 44, 3800 (1979); Y. Sogah, A.C.S. Polym. Repr. 1988, No. 2, 3; J.W. Mays, polym. Bull. 23, 247 (1990); IN THE. Khan et al. Macromolecules 21, 2684 (1988); A. Morikawa, Macromolecules 24, 3469 (1991); Akira Ueda, Susumu Nagai, Polymer 39, 202 (1990); T. Otsu, Polym. Bull. 11, 135 (1984); etc.

Process for the preparation of star block copolymers are also described in the following references: W.J. Burlant, A.S. Hoffman, "Block and Graft Polymers" (1960, Renhold); R.J. Ceresa, "Block and Graft Copolymers" (1962, Butterworths); L. C. Allport, W.H. James, "Block Copolymers"  (1972, Applied Sci.); A. Noshay, J.E. McGrath, "Block Copoly mers "(1977, Academic Press), etc.

Furthermore, the star-shaped copolymer described in the before underlying invention is used by a known Process for the preparation of star-shaped polymers Herge be prepared, in which monomers with one or more pola ren groups and one or more groups that polymerize contained double bonds. Examples for the known method include a polymerization, in which a carbanion is used as an initiator. concrete Examples of these methods are in the following litera described: M. Morton, T.E. Helminiak et al., J. Polym. Sci. 57, 471 (1962); Gordon III, M. Blumenthal, J.E. Loftus et al., Polym. Bull. 11, 349 (1984); R. B. Bates, W. A. Beavers et al., J. Org. Chem. 44, 3800 (1979).

For the preparation of the polymer (P), the special polar Groups, such as B. -COOH, in the segment (Y), the should polar groups in the corresponding monomers by a Protected group and becomes a block copolymer prepared by a living polymerization reaction, such as z. As an ionic polymerization by organic Metallver compounds (such as, for example, alkyl lithium compounds, lithium diiso propylamide, alkyl magnesium halides) or iodine water substance / iodine or photopolymerization, in which a porphyrin Metal complex is used as a catalyst, or by Gruppenübergangspolymerisation.

After the polymerization reaction, the protecting group should by hydrolysis, hydrogenation, oxidative degradation or photoche mix decomposition are released. An example of this Reactions is represented by the following scheme:

Release of the protective group
R _f : alkyl group substituted by one or more fluorine atoms
R: an alkyl group (such as the residue of a porphyrin ring)
Prep: protecting group (such as -C (C ₆ H ₅ ) ₃ , -Si (C ₃ H ₇ ) ₃ )
b: indicates that the units linked with "b" form a block to form a block copolymer.

The macromonomers corresponding to the macromonomer segments (M _A ) and (M _B ) and the polymer (P) comprising at least one of these macromonomer segments (M _A ) and (M _B ) can be prepared by known polymerization methods.

For example, macromonomers can be prepared by reacting a polymer having a weight average molecular weight of not more than 2 × 10 ⁴ by known polymerization methods, such as. For example, ionic polymerization with organic metal compounds (such as alkyllithium compounds, lithium diisopropylamide and alkylmagnesium halides) or iodine hydrogen / iodine, photopolymerization wherein a porphyrin-metal complex is used as the catalyst, group transfer polymerization, photoinitiator polymerization in which a dithiocarbamate compound or a xanthate compound is used as an initiator, radical polymerizations using radical initiators (such as azobis compounds and peroxide compounds) and chain transfer agents (such as mercapto compounds and iodine compounds) are prepared and then mixed with various reagents Group with polymerizable double bond to one end of the resulting polymer ties.

For example, The living polymers can easily penetrate through the fol prepared by the literature described P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984); B.C. Anderson, G.D. Andrews et al., Macromolecules 14, 1601 (1981); K. Hatada, K. Ute et al., Polym. J. 17, 977 (1985), 18, 1037 (1986); Koichi Migite, Koichi Hatada, Ko bunshikako 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Papers for Polymer 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc. 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Yukigoseikagaku 43, 300 (1985); D. Y. Sogah, W.R. Hert ler et al., Macromolecules 20, 1473 (1987); Takayuki Otsu, Polymer 37, 248 (1988); Shunichi Hinoemori, Takaiti Otsu, Polym. Rep. Jap. 37, 3508 (1988); JP-A-64-111 and 64-26619.

Examples of radical polymerization processes are described in: Y. Yamashita, J. Appl. Polym. Sci. Appl. Polym. Symp. 36, 193 (1981); K.K. Roy et al., Makromol. Chem.  153, 71 (1972); Y. Yamashita et al., Polym. J. 14, 255 (1982); Akira Ueda, Susumu Nagai, Kagaku to Kogyo 60, 57 (1986).

Process for introducing the polymerizable group Double bond in one end of the polymer are on this Ge known area. Such methods are for. In the following References and the references cited therein be written: P. Dreyfuss, R. P. Quirk, Encycl. Polym. Sci. Closely. 7, 551 (1987); P.F. Rempp, E. Franta, Adv. Polym. Sci. 58, 1 (1984); V. Percec, Appl. Poly. Sci. 285, 95 (1984); R. Asami, M. Takari, Macromol. Chem. Suppl. 12, 163 (1985); P. Rempp et al., Macromol. Chem. Suppl. 8, 3 (1984); Yushi Kawakami, Chemical Industry 38, 56 (1987); Yuya Yamashita, Polymer 31, 988 (1982); Shiro Kobayashi, Polymer 30, 625 (1981); Toshino Bu Higashimura, Journal of Japan Adhesive Society 18, 536 (1982); Koichi Ito, Polymer Processing 35, 262 (1986); Shiro Toki, Takashi Tsuda, Functional Materials, 1987, No. 10, 5; Yuya Yamashita, "Chemistry and Industry of Macromonomer" (1989, I.P.C. Co., Ltd.).

For preparing the above-mentioned macromonomer with spe In the case of major polar groups, the polar groups should be included in the corresponding monomers are protected by protective groups and the protecting groups should after the polymerization and Introduction of polymerizable double bond group be removed.

The protection by protecting groups and the release of the Protecting groups can be readily determined by known techniques ken be performed. Such methods are additional to the above references in the following literature described: Yoshio Iwakura, Keisuke Kurita, "Reacti Polymer, Kodansha Co., Ltd. (1977); T.W. Green, "Protec Organic Groups ", John Wiley & Sons (1981); J. F. W. McOmie, "Protective Groups in Organic Chemistry", Ple num Press 1973; etc.  

The polymer (P ₄ ) can also by known living poly polymerization process such. For example, ionic polymerization, Grup penübertragungspolymerisation, porphyrin metal polymerization tion and photoinitiator polymerization can be prepared.

The polymer (P ₄ ) can also be prepared by radical polymerization using azo initiators as described in the following references: Akira Ueda, Susumu Nagai et al., Kobunshi Ronbunshu 33, 131 (1976); Akira Ueda, Susumu Nagai et al., Kagaku to Kogyo 64, 446 (1990).

The polymer (Q)

In the following, the polymer (Q), that is, the polymer (Q ₁ ) and the polymer (Q ₂ ) will be described in more detail.

The polymer (Q ₁ )

As explained above, the polymer (Q ₁ ) is a low molecular weight polymer containing the units of the above-mentioned formula (I) and the above-mentioned polar group. The polar group may be contained in a substituent group at one end of the main chain of the polymer or in a repeating unit of the main chain.

When the polar group is contained both in the repeating unit of the main chain and in the substituent at one end of the main chain, the repeating unit having a polar group may e.g. In an amount of 0.05 to 10% by weight based on the total weight of the polymer (Q ₁ ) and is the sum of the weight of the repeating unit having the polar group and the weight of the substituent having the polar group z. B. 0.5 to 15 wt .-%, preferably 1 to 10 wt .-%. A total weight less than 0.5% by weight results in a lower initial potential, resulting in insufficient density of images, and a total weight exceeding 15% by weight results in poor dispersion properties, resulting in deterioration of image quality and contamination of the image Causes background even if the polymer (Q ₁ ) has a low molecular weight.

The unit of formula (I) is preferably the methacrylate unit with an aryl group, which is represented by the following For Meln (Ia) and (Ib) is shown:

wherein T ₁ and T _{2 are} each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, chlorine, bromine, -COR ₄ or -COOR ₅ (R ₄ and R ₅ each independently represent a hydrocarbon group having 1 to 10 carbon atoms and L ₁ and L ₂ each independently represents a single bond or a linking group having 1 to 4 atoms in a main chain.

The weight-average molecular weight of the polymer (Q ₁ ) is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ . The glass transition temperature of the polymer (Q ₁ ) is preferably in the range of -30 ° C to 110 ° C, in particular in the range of -20 ° C to 90 ° C.

A weight-average molecular weight below 1 × 10 ³ results in poorer coatability. A weight average molecular weight above 2 × 10 ⁴ results in a deterioration in the maintenance of charge in the dark and photosensitivity under severe conditions such. As high or low temperature and high or low humidity, whereby the effect according to the invention, ie a stable image reproduction, can not be achieved sufficiently.

The units of the formula (I) may be contained therein in an amount of not less than 30% by weight, preferably 50 to 97% by weight, based on the total weight of the polymer (Q ₁ ).

The polymer (Q ₁ ) preferably contains the moiety of the formula (Ia) or (Ib) which comprises a methacrylate moiety having an unsubstituted benzene, unsubstituted naphthalene or benzene residue which is substituted by a specific substituent in the 2- and / or 6-position, and has a polar group at one end of the polymer.

In the following, the units of the formula (I) will be closer wrote.

Preferably, in the formula (I), a ₁ and a ₂ each independently represent the following: hydrogen, cyano, alkyl of 1 to 4 carbon atoms, such as. Methyl, ethyl, propyl and butyl, -COOR ⁸ or -Z-COOR ⁸ (R ⁸ = hydrogen or an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an aralkyl group of 7 to 18 carbon atoms, an alicyclic group having 3 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms which may be substituted with groups as mentioned above for R ³ ; Z = a hydrocarbon group such as methylene, ethylene and propylene).

R ³ is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms, such as. Methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradexyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl and 3-hydroxypropyl, an optionally substituted alkenyl group having 2 to 18 carbon atoms, such as. For example, vinyl, allyl, isopropenyl, butenyl, hexenyl, heptenyl and octenyl, an optionally substituted aralkyl group having 7 to 12 carbon atoms, such as. B. benzyl, phenethyl, Naphthylme methyl, 2-naphthylethyl, methoxybenzyl, ethoxybenzyl and Me methylbenzyl, an optionally substituted Cycloalkylgrup pe having 5 to 8 carbon atoms, such as. B. cyclopentyl, Cy clohexyl and cycloheptyl, or an optionally substituted aryl aryl group such. Phenyl, tolyl, xylyl, mesityl, naphthyl, methoxyphenyl, ethoxyphenyl, fluorophenyl, difluorophenyl, bomphenyl, chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl and cyanophenyl.

Preferably, T ₁ and T ₂ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 10 carbon atoms, such as. An alkyl group of 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and the like), an aralkyl group of 7 to 9 carbon atoms (such as benzyl, phenethyl, 3-phenylpropyl, chlorobenzyl, dichlorobenzyl, Bromobenzyl, methylbenzyl, methoxybenzyl and chloromethylbenzyl), an aryl group (such as phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl and dichlorophenyl) or -COR ₄ or -COOR ₅ (preferably R ₄ and R _{5 are} each independently of one another are hydrocarbyl groups given above as hydrocarbon groups of 1 to 10 carbon atoms).

Preferably, L ₁ and L ₂ in the formulas (Ia) and (Ib) are each independently a single bond or a linking group having 1 to 4 atoms in a Hauptket te, such as. B. - (CH ₂ ) _n1 - (n ₁ = an integer from 1 to 3), -CH ₂ O-CO-, -CH ₂ CH ₂ O-CO-, -CH ₂ CH ₂ O-, especially one Compound with 1 to 2 atoms in a main chain.

In the following examples of the units in the poly mers (Q ₁ ) are given, which should not be construed as limiting the present invention. In the following formulas (q-1) to (q-20), n is an integer of 1 to 4, m is 0 or an integer of 1 to 3, p ₁ is an integer of 1 to 3, R ₉ to R ₁₂ are each -C _n H _{2n + 1} or - (CH ₂ ) _m -C ₆ H ₅ (n and m are as defined above), X ₁ and X ₂ are the same or different and each represents Hydrogen, Cl, Br or I.

The following is the polar group that is in the itself homing unit in the main chain or in the substituent is included at the end of the main chain, explained in more detail.

The polar group may be selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, -PO (OH) R ₁ (R ₁ = a hydrocarbon group or -OR ₂ , wherein R _{2 is} a hydrocarbon group) and residues of cyclic anhydrides.

Preferably, R ₁ and R ₂ each represent an aliphatic group having 1 to 22 carbon atoms (such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl, allyl, crotonyl, butenyl and cyclohexyl), an aralkyl group having 7 to 22 carbon atoms (such as benzyl, phenethyl, 3-phenylpropyl, methylbenzyl, chlorobenzyl, fluorobenzyl, methoxybenzyl) or an optionally substituted aryl group, such as As phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorine phenyl, bromophenyl, chloromethylphenyl, dichlorophenyl, methoxyphenyl, cyanophenyl, acetamidophenyl, acetylphenyl and butoxyphenyl.

The remainder of a cyclic anhydride may be a residue of an ali phatic dicarboxylic acid anhydride or an aromatic Dicarboxylic anhydride.

Examples of aliphatic dicarboxylic acid anhydrides include a succinic anhydride, glutaconic anhydride, maleic acid anhydride, cyclopentane, 1,2-dicarboxylic anhydride, cyclo hexane-1,2-dicarboxylic anhydride and 2,3-bicyclo [2.2.2] octane dicarboxylic anhydride, which may be substituted, e.g. B. by a halogen atom such as chlorine and bromine or an alkyl group pe such as methyl, ethyl, butyl and hexyl.

Examples of aromatic dicarboxylic acid anhydrides include a: cyclic phthalic anhydride, cyclic naphthalenedi  carboxylic anhydride, pyridinedicarboxylic anhydride and thio phendicarboxylic anhydride, these cyclic anhydrides may be substituted, for. B. by a halogen atom such as Chlorine and bromine or an alkyl group such as methyl, ethyl, pro pyl and butyl, a hydroxyl group, a cyano group, a Nitro group and an alkoxycarbonyl group (such as methoxy carbonyl, ethoxycarbonyl and the like).

The polar group may be attached directly or through a linking group to one end of the main chain of the polymer (Q ₁ ). Examples of linking groups include: the group represented by the formula - (C (d ₁ ) (d ₂ )) - (d ₁ and d ₂ , the same or different from each other, each represent hydrogen, halogen (such as e.g. Chlorine and bromine), -OH, cyano, alkyl (such as methyl, ethyl, 2-chloroethyl, 2-hydroxyethyl, propyl, butyl and hexyl), an aralkyl group (such as benzyl and phenethyl) and phenyl ); - (CH (d ₃ ) -CH (d ₄ )) - (d ₃ and d _{4 may have the} same meanings as given above for d ₁ and d ₂ ); a cyclohexene group; a phenylene group; -O-; -S-; -N (d ₅ ) - (d ₅ is a hydrogen atom or a hydrocarbon group, such as a hydrocarbon group having 1 to 12 carbon atoms (such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, 2 -Methoxyethyl, 2-chloroethyl, 2-cyanoethyl, benzyl, methylbenzyl, phenethyl, phenyl, tolyl, chlorophenyl, methoxyphene 99999 00070 552 001000280000000200012000285919988800040 0002004306047 00004 99880yl and butylphenyl)); CO-; -COO-; -OCO-; -CON (d ₅ ) -; -SO ₂ N (d ₅ ) -; -SO ₂ -; -NHCONH-; -NHCOO-; -NHSO ₂ -; -CONHCOO-; -CONHCONH-; Groups of heterocyclic groups with 5 to 6 ring members which contain at least one hetero atom such. As oxygen, sulfur and nitrogen, and condensates thereof, such as. Thiophene, pyridine, furan, imidazole, piperidine and morpholine; or -Si (d ₆ ) (d ₇ ) - (d ₆ and d ₇ , the same or different from each other, each represents a hydrocarbon group or -Od ₈ (d ₈ is a hydrocarbon group as indicated above for d ₅ ) ). The linking group may exist alone or in combination.

The polymer (Q ₁ ) may contain units other than the unit of the formula (I).

Preferably, the polymer (Q ₁ ) may contain units with one or more polar groups.

The units with one or more polar groups can any units that have vinyl compounds with these correspond to polar groups copolyme with a monomer which is a unit of formula (I) which has a Unit of the formula (Ia) or (Ib) contains corresponds. The Vinyl compounds are for. As described in Polymer Society of Japan, "Polymer Data Handbook (Fundamentals)", published by Baifukan, (1986). Examples of these compounds include acrylic, α- and / or β-substituted acrylic acid (such as, for example, α-acetoxyacrylic acid, α-acetoxymethylacrylic acid re, α- (2-amino) methylacrylic acid, α-chloroacrylic acid, α-bromo acrylic acid, α-fluoroacrylic acid, α-tributylsilylacrylic acid, α-cyanoacrylic acid, β-chloroacrylic acid, β-bromoacrylic acid, α- Chloro-β-methoxy- and α, β-dichloroacrylic acid), methacrylic acid, Itaconic acid, half ester of itaconic acid, half amides of itacon acid, crotonic acid, 2-alkenylcarboxylic acids (such as 2-pentene acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexene acid, 4-ethyl-2-octenoic acid), maleic acid, half ester of Maleic acid, hemiamides of maleic acid, vinylbenzenecarboxylic acid re, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphone acid, vinyl or allyl half-esters of dicarboxylic acids and Esters and amides of these carboxylic acids and sulfonic acids, wherein the esters and amides thereof one or more polar groups as substituents.

Examples of the units having one or more polar groups include units having the following formulas (b-1) to (b-52). In these formulas, e _{1 represents} a hydrogen atom or -CH ₃ , e _{2 represents} a hydrogen atom, -CH ₃ or -CH ₂ COOCH ₃ , R ₁₄ is an alkyl group having 1 to 4 carbon atoms, R ₁₅ is an alkyl group with 1 c is an integer of 1 to 3, d is an integer of 2 to 11, e is an integer of 1 to 11, f is an integer of 2 to 4, and g is carbon atom, benzyl or phenyl is an integer from 2 to 10.

The polymer (Q ₁ ) may contain units having one or more photocuring and / or thermosetting groups in addition to the unit of formula (I) and the units having one or more polar groups.

The units having one or more light-curing and / or thermosetting groups may be contained therein in an amount of not more than 20% by weight based on the total weight of the polymer (Q ₁ ). More than 20% by weight of these units result in poorer electrophotographic properties.

Examples of other moieties include residues of Me thacrylates, acrylic esters and crotonic acid esters with one or more groups coming from the above for the Substituent groups in the formula (I) mentioned ver are divorced; Residues of α-olefins; Remains of vinyl esters a carboxylic acid or acrylic acid (where the carboxylic acid is e.g. Acetic acid, propionic acid, butyric acid, valeric acid, benzoin acid and naphthalenecarboxylic acid may be); Remains of acrylic nitrile or methacrylonitrile; Residues of vinyl ethers; Remains of Itaconic acid esters (such as dimethyl esters and diethyl esters) residues of acrylamides; Residues of methacrylamides; Residues of styrenes (such as styrene, vinyltoluene, chlorsty rol, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxy carbonylstyrene, methanesulfonyloxystyrene and vinylnaphthalene); Residues of compounds with vinylsulfone group; Remains of Ver compounds with vinyl ketone group; Residues of heterocyclic Compounds with vinyl groups (such as vinylpyrrolidone,  Vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole and Vinyloxazine). However, the present invention is not on these examples are limited.

The above other units may preferably be contained therein in an amount of less than 30% by weight based on the total weight of the polymer (Q ₁ ).

Methods for introducing the polar group into one end of the main chain of the polymer (Q ₁ ) include: A method in which one end of the living polymer obtained by known anionic or cationic polymerization is reacted with various reagents (ie, an ioni nice polymerization reaction method); a method by radical polymerization by a polymerization initiator and / or a chain transfer agent having a specific polar group therein, or a method of combining the polymer obtained by the above method with polymers having a reactive group (such as amino group, halogen, epoxy group and the radical an acid halide group).

Examples of the above methods are e.g. In the following References and the references cited therein described: P. Dreyfuss, R.P. Quirk, Encycl. Polym. Sci. Closely. 7, 551 (1987); Yoshiki Nakajo, Yuya Yamashita, "Senryo to Yakuhin "30, 232 (1985); Akira Ueda, Susumu Nagai," Kagaku to Kogyo "60, 57 (1986).

Examples of the chain transfer agent used in the above mentioned method include: Mercapto Compounds with the polar group or the above reactive Group that can generate the polar group (eg, a remainder of Thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercap topropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid Re, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid,  3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-Mercap toethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2- Mercaptoethanesulfonic acid, 3-butanesulfonic acid, 2-mercaptoetha nol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3 Mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2- Mercaptoimidazole, 2-mercapto-3-pyridinol, 4- (2-Methyloxycar bonyl) phthalic anhydride, 2-mercaptoethylphosphonic acid anhy tride, 2-mercaptoethylphosphonic acid monomethyl ester), or iodine alkyl compounds having the above polar group or the above substituent group (such as, for example, iodoacetic acid, iodoprop pionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropro pansulfonsäure).

Examples of the polymerization initiator with the reactive Group include 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis (2-cya nopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2- methyl-N- (2-hydroxyethyl) propionamide), 2,2'-azobis (2-methyl N-1,1-bis (hydroxymethyl) -2-hydroxyethylpropionamide], 2,2'- Azobis [2- (1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane], 2,2'- Azobis [2- (2-imidazolin-2-yl) propane] and 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane].

The above-mentioned chain transfer agent or Polymerisa tion initiators can be used in an amount of 0.5 to 15 wt .-%, preferably 2 to 10 wt .-%, based on the weight of or the monomers used.

The polymer (Q ₂ )

As explained above, the polymer (Q ₂ ) is a type AB or ABA block copolymer containing the segment (M) containing at least the units of the formula (I) and containing no units with polar groups, and the segment (FIG. N) with the special polar groups.

The segment (N) contains the units with the polar group in an amount of z. B. 0.05 to 15 wt .-%, preferably 0.1 to 10 wt .-%, based on the total weight of the polymer (Q ₂ ). Less than 0.05% by weight results in a lower initial potential, resulting in insufficient image density, and over 15% by weight leads to poor dispersion properties, resulting in deterioration of the uniformity of the coating and the electrophotographic properties under high Temperature or Feuchtigkeitsbedin conditions entails and when used as an offset master causes contamination of the background.

The weight-average molecular weight of the polymer (Q ₂ ) is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ .

Less than 1 × 10 ³ and more than 2 × 10 ⁴ in the weight average molecular weight lead to a deterioration of the electrophotographic properties, whereby the inven tion proper effect can not be achieved to a sufficient extent.

The glass transition temperature of the polymer (Q ₂ ) is preferably from -30 ° C to 100 ° C, in particular 0 ° C to 90 ° C.

The segment (M)

The segment (M) contains the above-mentioned unit of the formula (I) z. B. in an amount of 30 to 100 wt .-%, preferably 50 to 100% by weight.

Preferably, a ¹ and a ² in the formula (I) are each hydrogen, halogen (such as fluorine, chlorine and bromine), cyano or a hydrocarbon group (e.g., an aliphatic group having 1 to 8 carbon atoms such as Methyl, ethyl, propyl, butyl, pentyl and hexyl; benzyl; or an aromatic group having 6 to 12 carbon atoms, such as phenyl). More preferably, a ^{1 is} a hydrogen atom and a ^{2 is} a methyl group.

R ³ is alkyl, aralkyl or an aromatic ring, preferably an aralkyl group with benzene ring or Naph thalinring or an aromatic ring.

R ³ is preferably a hydrocarbon group of 1 to 18 carbon atoms which may be substituted. The substituent group for R ³ may be any group other than the polar group contained in the segment (N), e.g. A halogen atom (such as fluorine, chlorine and bromine), -OR ⁵ , -COOR ⁵ or -OCOR ⁵ (wherein R ^{5 represents} a hydrocarbon group of 1 to 22 carbon atoms such as methyl, ethyl, propyl, butyl, Hexyl, octyl, decyl, dodexyl, hexadecyl and octadecyl). Preferably, the hydrocarbyl group is an optionally substituted alkyl group of 1 to 18 carbon atoms (such as methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, dexyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2 Cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl and 3-bromopropyl); an optionally substituted alkenyl group having 4 to 18 carbon atoms (such as, for example, 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2- Hexenyl and 4-methyl-2-hexenyl); an optionally substituted aralkyl group having 7 to 12 carbon atoms (such as benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl and dimethoxybenzyl); a given substituted alicyclic group having 5 to 8 carbon atoms (such as cyclohexyl, 2-cyclohexylethyl and 2-cyclopentylethyl); or an optionally substituted aromatic group having 6 to 12 carbon atoms (such as (phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, Acetylphenyl, methoxycarbonylphenyl, acetamidophenyl, propionamidophenyl and dodecyloylamidophenyl).

The units of the formula (I) which contain R ³ are preferably the units which have been mentioned above in connection with the polymer (Q ₁ ) as preferred units of the formulas (Ia) and / or (Ib). Preferred examples of substituent groups in the formulas (Ia) and (Ib) and concrete examples of the units of the formulas (Ia) and (Ib) may be the same as defined above for the polymer (Q ₁ ).

Other units in segment (M) may be units represented by formula (XII):
- (CH (m ¹ ) -C (m ² ) (X ¹ R ¹ )) -, where X ^{1 is} -CO-O-, -O-CO-, - (CH ₂ ) _p -CO-O-, - (CH ₂ ) _p -O-CO- (p = an integer of 1 to 3), -O-, -SO ₂ -, -CO-, -CON (R ² ) -, -SO ₂ N (R ² ) -, -CONHCO-O-, -CONHCONH- or -C ₆ H ₄ - is (R ² = hydrogen or hydrocarbon group), R ^{1 represents} a hydrocarbon group, m ¹ and m ^{2 are the} same or different and each have the same meaning have as stated above for a ¹ and a ² in formula (I).

A hydrocarbon group for R ² is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (such as, for example, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadexyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl and 3-bromopropyl); an optionally substituted alkenyl group having 4 to 18 carbon atoms (such as 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentynyl, 1-pentenyl, 1-hexenyl, 2 Hexenyl and 4-methyl-2-hexynyl); an optionally substituted aralkyl group having 7 to 12 carbon atoms (such as benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl and dimethoxybenzyl); an optionally substituted alicyclic group having 5 to 8 carbon atoms (such as cyclohexyl, 2-cyclohexylethyl and 2-cyclopentylethyl); or an optionally substituted aromatic group having 6 to 12 carbon atoms (such as phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyano-phenyl , Acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propionamidophenyl and dodecyloylamidophenyl).

If X ^{1 is} -C ₆ H ₄ -, the benzene ring may be substituted. The substituent groups may, for. A halogen atom (such as chlorine and bromine), an alkyl group (such as methyl, ethyl, propyl, butyl, chloromethyl and methoxymethyl) or an alkoxy group (such as methoxy, ethoxy, propoxy and Butoxy).

Preferred examples of R ¹ include a given substituted alkyl group having 1 to 22 carbon atoms (such as methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octa decyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl and 3-bromopropyl); an optionally substituted alkenyl group having 4 to 18 carbon atoms (such as 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2 Hexenyl and 4-methyl-2-hexenyl); an optionally substituted aralkyl group having 7 to 12 carbon atoms (such as benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl and dimethoxybenzyl); a given substituted alicyclic group having 5 to 8 carbon atoms (such as cyclohexyl, 2-cyclohexylethyl and 2-cyclopentylethyl); an optionally substituted aromatic group having 6 to 12 carbon atoms (such as phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl , Acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propionamidophenyl and dodecyloylamidophenyl).

X ^{1 is} particularly preferably -CO-O-, -O-CO-, -CH ₂ O-CO-, -CH ₂ CO-O-, -O-, -CONH-, -SO ₂ NH- or -C ₆ H ₄ -.

The following other units can be used together with the ones units of the formula (XII) also in the segment (M) enthal be: units that correspond to the monomer that with the monomer corresponding to the units of the formula (XII), can copolymerize, such as. B. units which are acrylonitrile, Methacrylonitrile and a heterocyclic compound with Vinyl group (such as vinylpyrrolidone, vinylpyridine, vinyli midazole, vinyl thiophene, vinyl pyrazole, vinyl dioxane and vinyl loxazine). These units can be in a crowd of not more than 20% by weight based on the total weight all units in the segment (M) included in this segment his.

The segment (N)

In the following, the segment (N) in the polymer (Q ₂ ) closer he explained.

The segment (N) contains at least one polar group selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, -PO (OH) R ¹ and residues of cyclic acid anhydrides.

R ¹ represents a hydrocarbon group or -OR ² (R ² is a hydrocarbon group) and preferably R ¹ and R ² each represent a hydrocarbon group having 1 to 6 carbon atoms which may be substituted (such as methyl, ethyl, Propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl, 2-methoxybutyl, benzyl, phenyl, propenyl, methoxymethyl, ethoxymethyl and 2-ethoxyethyl).

The remainder of a cyclic anhydride may be the same as defined above for the polymer (Q ₁ ). Examples of an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride may be the same as defined above for the polymer (Q ₁ ).

The units having one or more polar groups and examples thereof may also be the same as defined above for the polymer (Q ₁ ).

More than one type of units with the special polar Group, as mentioned above, may be in the segment (N) be included. In this case, the units in Form of a random sequence or in blocks in the Segment (N) to be included.

Further, in the segment (N), units other than the units having polar groups may be contained. Preferably, these units are those units of formula (I) mentioned above. However, these units may also be units other than the above other units given for the polymer (Q ₁ ) and may be in an amount of not more than 20% by weight based on the total weight of the segment (N) to be included in this segment.

The polymer (Q ₂ ) can be prepared by known polymerization methods. For example, the polymer (Q ₂ ) can be prepared by a method in which the polar group in monomers corresponding to a specific unit is protected with a protective group, and the protective group is formed by hydrolysis, hydrogenation, oxidative degradation or photochemical degradation after the preparation of a block copolymer by known living polymerizations such. For example, ionic polymerizations using organic metal compounds (such as alkyllithium compounds, lithium diisopropylamide and alkylmagnesium halides) or hydrogen iodide / iodine or photopolymerizations using a porphyrin metal complex as a catalyst or group transfer polymerizations are removed. An example of these reactions is illustrated in the following reaction scheme.

R: alkyl group, remainder of a porphyrin ring and the like
(Prep): protecting group (such as -C (C ₆ H ₅ ) ₃ , -Si (C ₃ H ₇ ) ₃ and the like
-b-: block connection.

For example, these methods are in the following references described: P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984); B.C. Anderson, G.D. Andrews et al., Macromolecules 14, 1601 (1981); K. Hatada, K. Ute et al., Polym. J. 17, 977 (1985), 18, 1037 (1986); Koichi Migite, Koichi Hatada, Ko bunshikako 36, 366 (1987); Toshinobu Higashimura, Nitsuo Sawamoto, Papers for Polymer 46, 189 (1989); N. Kuroki, T. Aida, J. Am. Chem. Soc. 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Yukigoseikagaku 43, 300 (1985); D. Y. Sogah, W.R. Hert Ler et al., Macromolecules 20, 1473 (1987).

Further, the polymer (Q ₂ ) can be prepared by using a monomer having an unprotected polar group by polymerization under light irradiation using dithiocarbamate compounds or xanthate compounds as an initiator. This process is described in the following references: Takayuki Otsu, Polymer 37, 248 (1988); Shunichi Hinoemori, Takaiti Otsu, Polym. Rep. Jap. 37, 3508 (1988); JP-A-64-111 and 64-26619; N. Higashi et al., Polymer Preprints, Japan, 36 (6), 1511 (1987); N. Niwa, J. Macromol. Sci. Chem. A24 (5), 567 (1987), etc.

The protection by the protecting group and the release of the Protecting group can easily be carried out by known methods be led. Such methods are also in the fol The following references are described: Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer", Kodansha Co., Ltd. (1977); T.W. Green, "Protective Groups in Organic Synthesis," John Wiley & Sons (1981); J. F. W. NcOmie, "Protective Groups in Organic  Chemistry ", Plenum Press (1973) etc.

Other processes for the preparation of block copolymers from Type AB are z. Example, a method in which an azobis compound (i.e., a high molecular weight azobis initiator) which is one of the Segments (M) and (N) is prepared, and then the monomers corresponding to the units making up the other segment exists, with the resulting connection polymerized by radical polymerization reaction become. The method is in the following references Akira Ueda et al., Papers for Polymer 44, 469 (1987); Akira Ueda, Reports by Osaka City Industrial Laboratory Tory 84 (1989).

The weight-average molecular weight of the high-molecular azobis initiator is preferably not more than 2 × 10 ⁴ , particularly considering the ease of preparation thereof and the regularity of the polymerization to obtain a block copolymer.

In the polymer (Q ₂ ) of the present invention, the segment (M) is preferably longer than the segment (N).

Accordingly, it is preferable to use the high-molecular azobis initiator containing the segment (N) when the polymer (Q ₂ ) is produced by this reaction. For example, the reaction is carried out according to the following reaction scheme:

The polymer (R)

In the following, the polymer (R), the at least one light hardening and / or thermosetting group contains, be wrote.

The photocuring and / or thermosetting group may be any to be a group. However, it can z. B. the above for the Polymer (P) mentioned groups in the polymer (R) may be included.  

The polymer (R) may be any polymer having light-curing and / or thermosetting group suitable for electrophotographi be used.

The polymer (R) may, for. B. from those in the following literature be described described: Takaharu Shibata, Jiro Isiwatari, Polymer 17, page 278 (1968); Sei Miyamoto, Hidehiko Takei, Imaging 1973, No.8; Koich Nakamura, "Practi cal Techniques or Binder for Recording Materials ", chapter 10, C.H.C. Co. ltd. (1985); "Denshishasinyo yukikankotai no genjo sinpojium, Yokoshu "(1985); Hiroshi Kokado," Recent Development and Utilization of Photoconductive Material and Photosensitive Material ", published by Nihonkagakujoho Co. ltd. (1986); Denshishashingakkai, "Denshishashingÿutu no kiso to oyo ", Chapter 5, Korona sha, (1988); D. Tatt, S.C. Heidecker, Tappi 49, No. 10, 439 (1966); IT. Baltazzi, R.G. Blanclotte et al., Phot. Sci. Closely. 16, No. 5, 354 (1972); Guen Chan Kei, Isamu Shimizu, Eiichi Inoue, Journal of Society of Electrophotographics of Japan 18, No. 2, 22 (1980).

Examples of the polymer (R) include: olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride Copolymers, vinyl alkanoate polymers and copolymers, allylal kanoate polymer and copolymers, polymers and copolymers of Styrene and derivatives thereof, butadiene-styrene copolymers, iso pren-styrene copolymers, butadiene-unsaturated carboxylate Copolymers, acrylonitrile copolymers, methacrylonitrile copolymers R, alkyl vinyl ether copolymers, acrylate polymers and copoly mers, methacrylate polymers and copolymers, styrene-acrylate Copolymers, styrene-methacrylate copolymers, itaconic acid ster polymers and copolymers, maleic anhydride copolymers acrylamide copolymers, methacrylamide copolymers, hydroxyl group-modified silicone resins, polycarbonate resins, ketone Resins, polyester resins, silicone resins, amide resins, hydroxy and carboxyl group-modified polyester resins, butyral Resins, polyvinyl acetal resins, cyclized rubber methacrylate lat copolymers, cyclized rubber-acrylic ester copolymers,  Copolymers containing heterocycles without a nitrogen atom (eg furan, Tetrahydrofuran, thiophene, dioxane, dioxofuran, lactone, benzo furan, benzothiophene and 1,3-dioxetane) and epoxy resins.

In the photoconductive layer of the present invention For example, in addition to the polymer (P), (Q) and (R), others Binder resins are used. Such other resins may be any resins that are known in electropho tographic materials, as with respect to the polymer (R) were used.

Light-curing and / or thermosetting agent. Preferably, the photoconductive layer of the invention according to electrophotographic material for color proofing Continue a small amount of a light-curing and / or heat hardening agent to the curing properties of the To improve coating. The term "light-curing and / or thermosetting agent "as used herein for a light-curing (s) and / or thermosetting compound (s) formation, oligomer and resin and a crosslinking agent.

The light-curing and / or thermosetting agent can in one Amount of z. B. 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, per 100 parts by weight of the total amount of poly mers (P), (Q) and (R) are used.

Less than 0.01 part by weight of light-curing and / or heat hardening agent leads to an insufficient improvement the hardening of the coating, while more than 20 parts by weight of it to an adverse effect on the electrophotographic Properties lead.

A photocuring and / or thermosetting resin may be any be a known curable resin, z. As the resins with hardness groups which are above for the segment (Y) of the polymer (P) were explained.  

The photocuring and / or thermosetting agent may include Crosslinking agent, which is generally in this field as a crosslinking agent, examples being here for z. B. in the following literature who described Shinzo Yamamoto, Tosuke Kaneko, "Crosslinking Agent Handbook ", published by Taiseisha (1981); Kobunshigak kai, "Polymer Data Handbook (Fundamentals)", Baifukan (1986).

Examples of crosslinking agents include: organic Silane compounds (such as a silane coupling agent such as Vinyltrimethoxysilane, vinyltributoxysilane, gamma-glycidoxy propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltriethyoxysilane), polyisocyanate compounds (such as tolylene diisocyanate, o-toluene diisocyanate, diphe nylmethane diisocyanate, triphenylmethane triisocyanate, polymethy lenpolyphenylisocyanat, hexamethylene diisocyanate, isophorone diisocyanate, polymeric polyisocyanates), polyols (such as 1,4- Butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane), polyamines (such as, for example, ethylenediamine, gamma-hydroxypropylethylenediamine, phenylenediamine, hexamethyl Lendiamin, N-aminoethylpiperazine, modified aliphatic Polyamines), polyepoxy group-containing compounds and epoxy Resins (such as those described in Hiroshi Kakiuchi, "Novel Epoxy Re sins ", Shokodo (1985), Kuniyuki Hashimoto," Epoxy Resins ", Nikkan Kogyo Newspaper Company (1969) melamine resins (such as those in Nitsuwa Ichiro, Hideo Natsunaga, "Urea Melamine Resins", Nikkan Kogyo Newspaper Company (1969)) and poly (meth) acrylate compounds (such as those in Haranobu Okawa, Takeo Saegusa, Toshinobu Higasimura, "Oligomer", Kodansha 1976; Eizo Omori, "Functional Acrylic Resin", Technosystem 1985 described compounds). Next can also be monomers with polyfunctional curable groups, such as. B. Vinyl methacrylate lat, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycoldiacrylate, divinylsuccinate, divinyl adipate, diallylsuc cinate, 2-methylvinylmethacrylate, trimethylolpropane trimeth acrylate, divinylbenzene and pentaerythritol polyacrylate  be set.

As explained above, the present invention is thereby characterized in that the photoconductive layer disclosed in Be Touching with a transfer layer, after the formation the photoconductive layer is cured by application. Accordingly, it is preferred to use the polymer (P), the polymer (Q) and the polymer (R) as well as the light-curing and / or heat to use hardening agents in a suitable combination, so that Each polymer may have functional groups that are chemically bind to each other.

Such combinations of functional groups are on well known in this field. For example, are combinations of funk tional groups in the following table as a combination of functional groups from group A and functional Groups from group B shown. This table should, however not considered as limiting the present invention become.  

Table 1

R is a hydrocarbon group. R ¹⁵ and R ¹⁶ are alkyl groups. R ¹⁷ to R ¹⁹ are alkyl or alkoxy groups, wherein at least one of R ¹⁷ to R ^{19 is} an alkoxy group. B ¹ and B ² are electron-withdrawing groups, such as. B. -CN, -CF ₃ , -COR ²⁰ , -COOR ²⁰ and -SO ₂ OR ²⁰ (R ²⁰ = hydrocarbon group, such as C _n H _{2n + 1} (n = an integer from 1 to 4) , -CH ₂ C ₆ H ₅ and -C ₆ H ₅ ).

Other additives

To the binder (Q) may optionally be a Reaktionsbe be given to accelerate the crosslinking reaction promote.

If the crosslinking reaction in the formation of chemical Bonds between functional groups, z. B. the following accelerators are used: Organic Acids (such as acetic acid, propionic acid, butyric acid, Ben cosulfonic acid and p-toluenesulfonic acid); Phenols (eg Phe nol, chlorophenol, nitrophenol, cyanophenol, bromophenol, naph thol and dichlorophenol); organometallic compounds (such as z. Zirconium acetylacetonate, zirconium acetylacetate, cobalta cetyl acetate and tin dibutoxydilaurate); dithiocarbamic compounds (such as salts of diethyl dithiocarbamic acid); Thiuram disulfide compounds (such as tetramethylthiuram disulfide fid); and carboxylic acid anhydrides (such as phthalic anhydride, Maleic anhydride, succinic anhydride, butylsuccin acid anhydride, 3,3 ', 4,4'-Benzophenontetracarbonsäuredianhy and trimellitic anhydride).

If the crosslinking reaction is a polymerization reaction is a polymerization initiator (such as peroxides and Azobis compounds).

The above-mentioned binder is applied after application Light and / or heat cured. The heat curing requires Stricter drying conditions than the conditions for  the production of conventional electrophotographic Materials are required. For example, be for drying a higher temperature and / or longer drying times needed. Alternatively, it is preferable to post the binder the drying of a coating solvent to heat. The heating can be carried out at a temperature of 60 ° C to 150 ° C for 5 to 120 minutes. Milder conditions are possible if the above-mentioned reaction accelerator is used.

Method for photocuring special functional groups pen of the resin of the present invention can with actini shear radiation.

The actinic radiation can be visible light, UV light, Light in the far UV range, electron radiation, X-ray rays, gamma rays, alpha rays and preferably UV rays Be radiation. Rays with a wavelength of 310 nm up to 500 nm is particularly preferred. In general, for the irradiation a mercury vapor lamp, a halogen lamp etc. used. The irradiation can z. B. from a Entfer from 5 to 50 cm for 10 seconds to 10 minutes.

Photoconductive compounds

The photoconductive compound described in the present Er can be used any organic or be inorganic compound.

For example, The compound may be a known inorganic photo conductive connection, such. As zinc oxide, titanium oxide, zinc sul fid, cadmium sulfide and lead sulfide. Zinc oxide and titanium oxide are taking into account the environmental impact before Trains t.

When an inorganic photoconductive compound, such as. B. Zinc oxide and titanium oxide is used, the Bindemit telharze preferably in an amount of 10 to 100 parts by weight,  in particular 15 to 40 parts by weight, based on 100 Parts by weight of the inorganic compound used.

Organic photoconductive compounds may be any be known compounds. For example, can those mentioned which are used in a photoconductive Layer comprising an organic photoconductive compound, a sensitizing dye and a binder resin includes and z. B. is described in: JP-B-37-17162 and 62- 51462; JP-A-52-2437, 54-19803, 56-107246 and 57-161863; one photoconductive layer containing a charge-generating agent, a charge transporting agent and a binder resin includes and z. B. is described in: JP-A-56-146145, 60-17751, 60-17752, 60-17760, 60-254142 and 62-54266; and a photo conductive layer of double-layer type, which is a charge generating agent and a charge transporting agent in contains different layers and z. B. is described in JP-A-60-230147, 60-230148 and 60-238853.

Examples of organic conductive compounds of the first Type include:

• a) triazole derivatives as described in US Patent 3,112,197;
• b) oxadiazole derivatives as described in U.S. Patent 3,189,447;
• c) imidazole derivatives as described in JP-B-37-16096;
• d) Polyarylalkane derivatives, as in US Pat. No. 3,615,402, 3,820,989 and 3542544, JP-B-45-555 and 51-10983, JP-A-51-93224, 55-108667, 55-156953 and 56-36656;
• e) pyrazoline or pyrazolone derivatives as described in US Pat. No. 3,180,729 and 4278746; JP-A-55-88064, 55-88065, 49-105537, 55- 51086, 56-80051, 56-88141, 57-45545, 54-112637 and 55-74546;
• f) phenylenediamine derivatives as described in U.S. Patent 3,615,404; JP-B- 51-10105, 46-3712 and 47-28336; JP-A-54-83435, 54-110836 and 54-119925;
• g) arylamine derivatives as described in US Patent 3,567,450; 3180703, 3240597, 3658520, 4232103, 4175961 and 4012376; JP-B- 49-35702; DE-AS-1110518; JP-B-39-27577; JP-A-55-144250,  56-119132 and 56-22437;
• h) Amino-substituted chalcone derivatives as described in US Pat Described 3526501;
• i) N, N-bicarbazyl derivatives as described in US Pat. No. 3,542,546 ben;
• i) oxazole derivatives as described in U.S. Patent No. 3,257,203;
• k) styryl-anthracene derivatives as described in JP-A-56-46234 ben;
• l) fluorenone derivatives as described in JP-A-54-110837;
• m) hydrazone derivatives as described in U.S. Patent 3,717,462; JP-A-54-59143 (according to US-PS 4150987), 55-52063, 55-52064, 55- 46760, 55-85495, 57-11350, 57-148749 and 57-104144 described;
• n) benzidine derivatives as described in U.S. Patent 4,047,948; 4047949, 4265990, 4273846, 4299897 and 4306008;
• o) stilbene derivatives as described in JP-A-58-190953, 59-95540, 59-97148, 59-195658 and 62-36674;
• p) polyvinylcarbazole and derivatives thereof as described in JP-B- 34-109 66;
• q) vinyl polymers, such as. As polyvinylpyrene, polyvinyl anthracene, polyvinyl-2-vinyl-4- (4'-dimethylaminophenyl) 5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole as in JP-B-43-18674 and 43-19192;
• r) polymers, such as. Polyacenaphthylene, polyindene and Co polymers of acenaphthylene with styrene, as described in JP-B- 43-19 193;
• s) condensation polymers, such as. Pyrene-formaldehyde resins, Brompyren-formaldehyde resins and ethylcarbazole formaldehyde hyd resins as described in JP-A-56-13940;
• t) Triphenylmethanpolymere, such as. For example, JP-A-56-90833 and 56-161550.

The organic photoconductive compounds should not is restricted to the above compounds (a) to (t) Be and can any known organic photo be conductive compounds. You can be alone or in Combination of two or more of them or two or more  Species are used.

As a charge-generating agent in the photoconductive layer Can all known organic and inorganic charge generating agents operating in the field of electrophotogra are known, are used. at games for the charge-generating agents include selenium, Selenium tellurium, cadmium sulfide, zinc oxide and the following orga niche pigments:

• 1) Azo pigments, such as. Monoazo, bisazo and tris zo-pigments, such as. In U.S. Patents 4,436,800 and 4,439,506; JP-A-47-37543, 58-123541, 58-192042, 58-219263, 59-78356, 60-179746, 61-148453 and 61-238063; JP-B- 60-594 1 and 60-45664;
• 2) phthalocyanine pigments, such as. B. non-metallic or metallic phthalocyanines, such as. In US-PS 3397086 and 4666802; JP-A-51-90827 and 52-55643;
• 3) perylene pigments, such as. In US Patent 3371884 and JP-A 47-30330;
• 4) indigo and thioindigo pigments, such as. In GB-PS 2237680 and JP-A-47-30331;
• 5) quinacridone pigments, such as. B. in GB-PS 2237680 and JP-A-47-30332;
• 6) polycyclic quinone pigments, such as. B. described in British Patent 22376789 and JP-A-59-184348, 62-28738 and 47-18544;
• 7) Bisbenzimidazole pigments, such as. As described in JP-A- 47-30331 and 47-18543;
• 8) Squarium pigments as disclosed in U.S. Patent Nos. 4,396,610 and 4,644,082 wrote;
• 9) Azulenium pigments as described in JP-A-59-53850 and 61-21254 be wrote.

The above-mentioned pigments may be used singly or in combination tion of two or more of them.

The ratio of organic photoconductive compound to Binder depends on the compatibility of these two compo  from. That is, the upper limit of the amount of organic Photoconductive compound depends on the compatibility of the photoconductive compound with the binder from and a Excess of organic photoconductive compound results a crystallization of the same. Since the electrophotographi sensitivity is proportional to the amount of photoconductive higer connection decreases, preferably just as much organic photoconductive compound provided that these Compound not crystallized. The organic photoconduct capable connection can z. B. in an amount of 5 to 120 Parts by weight, preferably 10 to 100 parts by weight, per 100 Parts by weight of binder may be present. The organic photo conductive compound can be used singly or in combination be set.

sensitizing dyes

In the electrophotographic material of the present invention for Color proof can depend on the light source for the exposure, such. B. visible light or Halbleiterla if necessary, any light of sensitization substances are used. Examples of such Sensibili cationic dyes include: carbonium dyes, di phenylmethane dyes, triphenylmethane dyes, xanthan Dyes, phthalein dyes, polymethine dyes (such as for example As oxonol dyes, merocyanine dyes, cyanine color substances, rhodacyanine dyes and styryl dyes) and Phthalocyanine dyes, which may contain metal atoms, and are z. As described in the following references: Haruki Miyamoto, Hidehiko Takei, Imaging 1973, No. 8, p 12; C.J. Young et al., RCA Review 15, page 469 (1954); Kohei Kiyota, Denkitushingakkaironbun, J63-C, No.2, page 97 (1980); Yuji Harazaki et al., Kogyokagakuzasshi 66, p. 78 and 188 (1963); Tadaaki Tani, Nihonshashingakkai 35, page 208 (1972).

Examples of carbonium dyes, triphenylmethane dye Fe, xanthene dyes and phthalein dyes are found  z. In: JP-B-51-452; JP-A-50-90334, 50-114227, 53-39130 and 53-82353; U.S. Patents 3,052,540 and 4,054,450; JP-A-57-16456.

Examples of polymethine dyes, such as. B. oxonol color substances, merocyanine dyes, cyanine dyes and Rhoda cyanine dyes are for. As described in F.M. Harmmer, "The Cyanine Dyes and Related Compounds; U.S. Patent 3,047,384, 3,110,591, 3121008, 3125447, 3128179, 3132942 and 3622317; GB-PS 1226892, 1309274 and 14045898; and JP-B-48-7814 and 55-18892.

Examples of polymethine dyes that are in the near infrared to infrared range with a wavelength of not less spectrally sensitized as 700 nm, z. B. described in JP-A-47-840 and 47-44180; JP-B-51-41061, 49-5034, 49-45122, 57-46245, 56-35141, 57-157254, 61-26044 and 61-27551; US-PS 3619154 and 4175956; and "Research Disclosure", 1982, 216, 117-118.

The electrophotographic material of the present invention is also because of its use because of its behavior sensitizing dye is not impaired.

Next, conventional additives for electrophotographi optional materials in the electrophotographic Materials of the present invention are used.

Such additives include, for. B. a chemical sensibi lisierungsmittel to improve the electrophotographic Sensitivity, a plasticizer or a surfactant for Ver improvement of the film properties.

Examples of chemical sensitizers include: Elek tronening compounds, such as. B. halogens, benzochi non, chloranil, fluoranil, bromanil, dinitrobenzene, anthra quinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachloro phthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone, Dinitrofluorenone, trinitrofluorenone, tetracyanoethylene;  Polyarylalkane compounds, hindered phenolic compounds, p-phenylenediamine compounds, as described, for. In the following References are described: Hiroshi Komon, "The Latest Development and Utilization of Photoconductive Materials and Photosensitive Materials ", Chapters 4 to 6, Publ Nihonkagakujouhou Co. Ltd. (1986); and Compounds described in JP-A-58-65439, 58-102239, 58-129439 and 62-71965 are described.

Examples of plasticizers that can be added to to improve the plasticity of the photoconductive layer, include: dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalylethyl glycolate and dimethyl glycol phthalate. The soft can be used in such an amount that the static properties of the photoconductive layer thereby not be affected.

The above-mentioned additives are usually added in an amount from 0.001 to 2.0 parts by weight per 100 parts by weight of the photo used conductive layer.

The photoconductive material is ground and in a System containing a binder, a solvent for it and a Additive comprises by procedures well-known in the art dispersed. For example, it is with a device such. B. one Ball mill, a Kady mill, a sand mill, a dyno Mill®, a paint shaker, a roller mill and an ul trasound dispersing device, as described in Solomon, "Chemistry of Paint ", etc., dispersed in the system.

Then it is applied to the substrate, for. B. with a rod coater, a reverse coater or a dye-coating apparatus, in an on amount suitable for a given pictorial material system  is what it is dried on.

For the dispersion of the photoconductive material turned put solvents can be any solvents, whose nature depends on such factors as e.g. B. the solubility of the Binder is determined. These solvents can be or used in combination.

In the following, the transfer layer will be explained in more detail.

The transfer layer comprises a thermoplastic resin having a weight average molecular weight of e.g. B. 1 × 10 ³ to 1 × 10 ⁶ , preferably 5 × 10 ⁴ to 5 × 10 ⁵ , and a glass transition temperature of z. B. 0 ° C to 100 ° C, preferably 20 to 85 ° C. The thermoplastic resin is preferably used in an amount of not less than 70% by weight, especially not less than 90% by weight, of the transfer layer.

Examples of the thermoplastic resin include vinyl chloride resins, polyolefin resins, olefin-styrene copolymers, Vinylalkanoate resins, polyester resins, polyether resins, acrylic Resins, cellulose resins and aliphatic acid-modified Cellulose resins.

These resins are z. In the following references wrote: Nikkankogyoshinbunsha, "Plastic Material Lecture", 1 to 18 (1961); Vinyl Department of Kinkikagakukyokai, "Po lyvinylchloride ", published by Nikkankogyoshinbunsha 1988; Eizo Omori, "Functionality of Acrylic Resin", publ released by Technosystem in 1985; Eiichiro Takiyama, "Poly ester Resin Handbook ", published by Nikkankogyoshinbun sha 1988; Kazuo Yumoto, "Saturated Polyester Resin Handbook", published by Nikkankogyoshinbunsha 1989; Polymer Socie Japan, "Polymer Data Handbook," Chapter 1, pub light by Baifukan 1986; Yuji Harazaki, "The Latest Handbook of Binder Technology ", Chapter 2, published by Sogogi  jutu Center 1985.

The thermoplastic resins may be used singly or in combination tion can be used.

The transfer layer may include other additives to the physical properties thereof, such as. B. the Be coating properties, film-forming properties and the Strength of the coating to improve. Examples of Additi We include plasticisers, such as B. above for the pho Tungsten layer were mentioned. The thickness of the transfer layer is usually 0.1 to 10 μm, preferably 0.5 to 5 μm.

The transfer layer may, for. B. by a conventional Coating process can be applied. For example, will the up using a coating solution containing a suitable compound, such as. B. one of the above, ent holds and a process such. B. a Beschichtungsver as described above for the photoconductive layer was written. In addition, the transmiss layer by a well-known in this field spray drying process are applied. The above Beschich Methods for the transfer layer are not as limiting.

Production of a color control print

The method for producing a color control print under Use of the electrophotographic according to the invention Material for Farbandruck is z. B. Runaway as follows leads. First, by a conventional electrophotogra phisches method an image to be reproduced on the formed photosensitive material. That is, the charge, imagewise exposure, development and fixation are accomplished by methods well known in the art guided. Any type of developer, such. B. a Trockenent  Winder or a liquid developer can be used.

Examples of this method are z. As described in: Gen Machida, "Recording Material and Photosensitive Resin", Sei 107 to 127 (1983); and Gakkaishuppan Center Co. Ltd., Imaging, Nos. 2 to 5, "Development.Fixing.Charging.Transfer in Electrophotography ".

A combination of a scanning exposure method in which the exposure based on a digital information under Use of a laser beam is performed, and one Development process using a liquid developer lers is effective as they help to form a picture of high Precision leads.

An example of the methods will be described in more detail below wrote. The electrophotographic material is using a resistance needle method given on a flatbed and sucked in from the back to fix it. The up Charge is performed with a charging device, such as z. B. such as those in the following references described: Electrophotographic Society of Japan, "Fun damental and Applications of Electrophotographic Technique ", Page 212ff, published by Corona Co. Ltd. on 15th of June 1963. In general, the Corotron or Scorotron Ver drive used. It is also preferable that the charging be conditions by feedback based on data Devices for determining the charging potential to control, so that the surface potential in a ge suitable area is located.

Then, a scanning exposure by means of laser radiate according to the way they appear on pages 254 ff of the above-mentioned reference is described by guided. First, the electrophotographic material using a dot pattern, that of the image for yellow was converted from four color separations, exposed.  

Then, with a liquid developer, a toner Ent winding done. That is, the charged and exposed Material is removed from the flatbed and by direct Flüs as described on pages 275ff of the above mentioned reference is developed. The kind The exposure depends on the way the toner is developed from. For example, For a reverse development, a negative Exposure performed. That is, an image area becomes a laser exposed to radiation and a development bias is attached so that a toner adsorbed on an image area can be brewed. The toner should have the same charge polarity as the image forming material after charging. For more detailed information, see pages 157ff referenced above.

To the excess developer after the development too remove, the electrophotographic material is ge squeezed and dried, as on page 283 of the above litera described turstelle. It is also preferred the material Rinse with a liquid carrier for the developer.

Finally, the above methods for each color, i. H. Magenta, Cyan and Black repeated to make a picture with four Produce colors on the electrophotographic material.

The toner image is passed through together with the transfer layer Transfer heat to regular printing paper to obtain a color To produce a control print.

Fig. 1 shows a device for heat transfer of a tragungsschicht on plain paper. The electrophotographic material is passed through a pair of rubber-coated metal rollers provided with a built-in heater at a proper pressing pressure. The tempera ture on the surface of the rollers can, for. B. 50 to 150 ° C, preferably 80 to 120 ° C, amount. The contact pressure between the rolls is generally 0.2 to 20 kgf / cm ² (kgf / cm ² ), preferably 0.5 to 10 kgf / cm ² . The Transportge speed can z. 0.1 to 100 mm / second, preferably 1 to 30 mm / second. The optimum values may be selected depending on the kind of the electrophotographic material, that is, the physical properties of the transfer layer, the photoconductive layer and the support.

Preferably, the temperature on the surface of the whale zen by known devices in the range defined above is maintained. A device for preheating and / or cooling can be placed in front of the heating rollers. Springs or air cylinders that use compressed air for pressing (not shown in Fig. 1) may also be attached to both ends of an axle of at least one of the rollers.

As described above, the addition of the polymer (P) to the photoconductive layer, the detachability of the photoconductive improve layer of the transfer layer. As He result can be a high quality color control without Color shift and incorrect transmission received who the.

The following are examples of the present invention described in detail, but not as a limitation the same may be understood.

In the formulas of the examples, the symbol "-b-" indicates that two block segments on the two sides of the icon are present in the form of blocks present to a To form block copolymer. That is, a through the formula with the The symbol "-b-" represented copolymer is not a stati nice copolymer but a block copolymer.  

Example P-101:

A solution of 70 g of methyl methacrylate, 20 g of methyl acrylate, 10 g of glycidyl methacrylate and 200 g of toluene was heated to 80 ° C in a stream of nitrogen. 10 g of polymer azobis initiator (PI-1) of the following formula was added thereto and then reacted for 8 hours. After the reaction, the reaction mixture was precipitated in 1.5 L of methanol. The resulting precipitate was then collected and dried. There were obtained 75 g of polymer (P-101) (Mw: 3 × 10 ⁴ ).

Example P-102:

A solution of 63 g of methyl methacrylate, 12.8 g of tri (dipropyl) Silylmethacrylat and 200 g of tetrahydrofuran was in a Nitrogen stream sufficiently degassed and then abge to -20 ° C. cools. 0.8 g of 1,1-diphenylbutyllithium was added and Implemented for 12 hours. Then a solution of 30 g of the monomer (M-1) having the formula:

CH ₂ = C (CH ₃ ) (COO (CH ₂ ) ₂ C ₈ F ₁₇ ) (M-1)

and 60 g of tetrahydrofuran, which had been degassed in a stream of nitrogen sufficient, and reacted for 8 hours. The resulting reaction mixture was cooled to 0 ° C, whereupon 10 ml of methanol was added and reacted for 30 minutes. Then, the polymerization was stopped and the silyl ester was deprotected. The resulting polymer solution was stirred until reaching 30 ° C, whereupon 3 ml of 30% ethanol solution of hydrogen chloride was added and stirred for an additional hour. Then the reaction mixture was evaporated under reduced pressure to half the amount and precipitated in one liter of petroleum ether. The resulting precipitate was collected and dried under reduced pressure. There were obtained 76 g of polymer (P-102) (Mw: 6.8 × 10 ⁴ ).

Example P-103:

A solution of 63.8 g of methyl methacrylate, 19.7 g of 2- (trifluoroacetyloxy) ethyl methacrylate, 0.5 g of (tetraphenylporphin ato) aluminum methyl and 200 g of methylene chloride was heated to 30 ° C in a stream of nitrogen. The resulting reaction mixture was irradiated from a distance of 25 cm through a glass filter with light from a 300 W xenon lamp and reacted for 20 hours. Then, 25 g of monomer (M-2) having the following formula was added thereto, and the reaction mixture was irradiated in the same manner as above for another 12 hours. Then, 3 g of methanol was added to the reaction mixture, which was then stirred for 30 minutes, whereupon the reaction was completed. 50 g of a 5 wt .-% solution of p-toluenesulfonic acid in tetrahydrofuran were zugege ben for the purpose of hydrolysis of the resulting reaction mixture zugege. The resulting mixture was added to 2 liters of methanol to precipitate the polymer, and the resulting precipitate was collected and dried. There were obtained 70 g of polymer (P-103) (Mw: 7 × 10 ⁴ ).

Example P-104:

A mixture of 48 g of ethyl methacrylate, 12 g of glycidyl methacrylate and 2.4 g of benzyl N, N-diethyldithiocarbamate was placed in a vessel, sealed under a stream of nitrogen, heated to 50 ° C and then from a distance of 10 cm for 6 hours irradiated with light from a 400 W high pressure mercury vapor lamp through a glass filter to perform photopolymerization. The resulting mixture was dissolved in 100 g of tetrahydrofuran, and 40 g of monomer (M-3) represented by the following formula was added in 100 g of tetrahydrofuran to the solution of the resulting reaction mixture. The vessel was purged with nitrogen and the irradiation continued for a further 10 hours. The resulting reaction mixture was added to one liter of methanol to precipitate the polymer, and the precipitate was collected and dried. There were obtained 73 g of polymer (P-104) (Mw: 8 × 10 ⁴ ).

Example P-105:

A mixture of 55 g of methyl methacrylate, 20 g of 3- (trimethoxy silyl) ethyl methacrylate and 1.0 g of benzyl isopropylxanthate was placed in a vessel in a stream of nitrogen, sealed, heated to 50 ° C and then co-stirred from a distance of 10 cm for 6 hours Light from a 400 W high-pressure mercury vapor lamp irradiated through a glass filter to perform a Pho topolymerisation. To prepare a 40% solution, tetrafuran was added to the resulting mixture, followed by the addition of 25 g of the monomer (M-4) having the following formula. The vessel was purged with nitrogen and then the irradiation was continued for a further 10 hours. The resulting reaction mixture was added to 2 liters of methanol to precipitate the polymer, and the precipitate was collected and dried. 63 g of polymer (P-105) were obtained (Mw: 6 × 10 ⁴ ).

Examples P-106 to P-114:

The polymers listed in Table 102 were prepared in a similar manner to Example P-105. The Mw value of the resulting polymers (polymers (P-106) to (P-114)) ranged from 6 × 10 ⁴ to 8 × 10 ⁴ .

Example P-115:

The procedures of Example P-104 were repeated except that 10 g of the initiator (I-2) having the following formula was used instead of the benzyl-N, N-diethyldithiocarbamate. The polymer (P-115) having a Mw of 8.3 × 10 ^{4 was} obtained.

Example P-116:

The procedures of Example P-105 were repeated except that instead of the benzyl isopropylxanthate, 12 g of the initiator (I-3) represented by the following formula was used. It was a polymer (P-116) with a Mw of 9.3 × 10 ⁴ he hold.

Examples P-117 to P-125:

The procedures of Example P-104 were repeated except that 14 g of the initiator (I-4) having the following formula and monomers corresponding to the units listed in Table 103 were used. Polymers (P-117) to (P-125) having Mw in the range of 7 × 10 ⁴ to 9 × 10 ^{4 were} obtained.

Table 103

Examples P-126 to P-134:

The procedures of Example P-116 were repeated except that 9.6 g of the initiator (I-5) having the following formula and monomers corresponding to the units shown in Table 104 below were used. The polymers (P-126) to (P-134) having Mw in the range of 8 × 10 ⁴ to 10 × 10 ^{4 were} obtained.

Examples P-135 to P-138:

A mixture of 40 g of monomers corresponding to the units listed in Table 105, 11 g of initiator (I-6) having the following formula and 40 g of tetrahydrofuran was placed under a stream of nitrogen in a vessel, verschlos sen, to 50 ° C. and then irradiated with light from a 400 W high pressure mercury vapor lamp from a distance of 10 cm for 12 hours through a glass filter to perform photopolymerization. To the reaction mixture were added 23 g of methyl methacrylate, 22 g of methyl acrylate and a 50 wt% solution of 15 g of glycidyl methacrylate in tetrahydrofuran. The vessel was purged with nitrogen and the irradiation was then carried out for a further 10 hours. The resulting reaction mixture was added to one liter of methanol to precipitate the polymer, and the precipitate was collected and dried. Polymers (P-135) to (P-138) having Mw in the range of 6 x 10 ⁴ to 8 x 10 ^{4 were} obtained.

Table 105

Example P-201:

A mixture of 57 g of methyl methacrylate, 28 g of methyl acrylate, 15 g of glycidyl methacrylate, 17.5 g of initiator (I'-1) having the following formula and 150 g of tetrahydrofuran was heated to 50 ° C in a stream of nitrogen. The resulting reaction mixture was irradiated from a 400-W high-pressure mercury vapor lamp through a glass filter from a distance of 10 cm for 10 hours to perform photopolymerization. The resulting reaction mixture was added to 1.5 L of methanol to precipitate the polymer, and the precipitate was collected and dried. There were obtained 72 g of polymer with a Mw of 4.0 × 10 ⁴ .

40 g of the polymer, 60 g of the monomer (M'-2) and 100 g Te trahydrofuran were in a stream of nitrogen to 50 ° C he warms. The resulting reaction mixture was irradiated in the manner described above for 15 hours. The resulting reaction mixture was added to 1.5 L of methanol to precipitate the polymer, and the precipitate was collected and dried. There were obtained 78 g of polymer (P-201) with a Mw of 6 × 10 ⁴ .

Examples P-202 to P-214:

The procedures of Example P-201 were repeated except that instead of 17.5 g of the initiator (I'-2), 0.031 mol of the initiators given in Table 202 were used. There were obtained 70 to 80 g of the polymers (P-202) to (P-214) having Mw in the range of 4 × 10 ⁴ to 6 × 10 ⁴ .

Examples P-215 to P-233:

The procedures of Example P-201 were repeated except that 60 g of the monomers corresponding to the units given in Table 203 below were used instead of 60 g of the monomer (M'-2). The resulting polymers (P-215) to (P-233) had Mw values in the range of 6 × 10 ⁴ to 7 × 10 ⁴ .

Table 203

Examples P-234 to P-240:

The procedures of Example P-201 were repeated except that a mixture of 70 g of methacrylate monomer, 30 g of monomers corresponding to the units given in Table 204, 15 g of initiator (I'-7) and 100 g of tetrahydrofuran was used. There were obtained 80 g of polymers having Mw values in the range of 6 × 10 ⁴ to 7 × 10 ⁴ .

Further, by using a mixture of 50 g of the resulting polymer, 50 g of monomers (M'-2) and 100 g of tetrahydrofuran in the same manner as in Example P-201, except that diethyl ether was used instead of methanol, polymerization was carried out , The Mw value of the resulting polymers (P-234) to (P-240) was in the range of 8 × 10 ⁴ to 10 × 10 ⁴ .

Table 204

Examples P-241 to P-254:

The procedures of Example P-201 were repeated to prepare the polymers shown in Table 205, except that instead of 17.5 g of initiator (I'-1), 10 g of initiator (I'-2) and instead of of methanol used as a solvent for the re-precipitation diethyl ether. The polymers (P-241) to (P-254) having Mw values in the range of 7 × 10 ⁴ to 9 × 10 ^{4 were} obtained.

Table 205

Example P-301:

A mixture of 60 g of methyl methacrylate, 30 g of macromonomer of the following formula, 10 g of diglycidyl methacrylate and 150 g of toluene was heated to 70 ° C in a stream of nitrogen. 1.0 g of 2,2'-azobisisobutyronitrile (AIBN) was added and the reaction was carried out for 4 hours. Then another 0.5 g of AIBN was added and the reaction was carried out for a further 4 hours. Thus, the polymer (P-301) having a Mw of 6.5 × 10 ^{4 was} obtained.

Examples P-302 to P-314:

The procedures of Example P-301 were repeated except that 30 g of the macromonomers shown in Table 302 were used instead of 30 g of the macromonomer M-301. The polymers (P-302) to (P-314) having Mw values in the range of 5 × 10 ⁴ to 8 × 10 ^{4 were} obtained. The Mw value of the macromonomers used is given in Table 302.

Table 302

Examples P-315 to P-325:

A mixture of monomers corresponding to the units given in Table 303, 25 g of macromonomer FM-0721 (Mw 1 × 10 ⁴ , made by Chisso Corporation) and 200 g of toluene were heated to 80 ° C in a stream of nitrogen.

Examples P-326 to P-337:

The procedures of Example P-301 were repeated except that a mixture of a monomer of the following formula (M-302), the macromonomers shown in Table 304 and 200 g of toluene was used. The polymers in (P-326) to (P-337) having an Nw value in the range of 6 × 10 ⁴ to 8 × 10 ^{4 were} obtained.

Example P-401:

A mixture of 50 g of monomer having the following formula, 0.5 g of initiator having the following formula and 50 g of tetrahydrofuran was placed in a stream of nitrogen in a vessel, ver closed, heated to 60 ° C and then from a distance of 10 cm Irradiated with light from a 400W high pressure mercury vapor lamp through a glass filter for 10 hours to perform photopolymerization. To this was added a mixture of 25 g of methyl methacrylate, 15 g of glycidyl methacrylate and 10 g of macromonomer (MB-401) and 50 g of tetrahydrofuran. Thereafter, the vessel was rinsed with nitrogen and the irradiation was carried out for a further 16 hours. The resulting reaction mixture was added to 1.0 L of methanol to precipitate the polymer, and the precipitate was collected and dried. 68 g of polymer (P-401) having a Mw of 6 × 10 ^{4 were} obtained.

Example P-402:

A mixture of 36 g of the monomer (A-402), 4 g Siloxanma cromonomer Praqcell FM-725 (manufactured by Chisso Corporation, Mw = 1 × 10 ⁴ ), 1.0 initiator (I-402) of the following formula and 50 g of tetrahydrofuran was added to a vessel under a stream of nitrogen and sealed and heated to 50 ° C. Then, the mixture was irradiated for 12 hours in the same manner as in Example P-401 to conduct a photopolymerization. A mixture of 24 g methyl methacrylate lat, 18 g methyl acrylate and 18 g glycidyl methacrylate and 60 g tetrahydrofuran was added to the resulting mixture. Thereafter, the vessel was purged with nitrogen and it was irradiated as in Example P-401 for a further 12 hours be.

The resulting reaction mixture was added to one liter of methanol to precipitate the polymer. The precipitate was washed and dried. There were obtained 70 g of polymer (P-402) having an Mw of 8 × 10 ⁴ .

Example P-403:

A mixture of 25 g of methyl methacrylate, 15 g of glycidyl meth acrylate, 10 g macromonomer (MB-402) with the following formula, 2.5 g initiator (I-403) having the following formula and 50 g Tetrahydrofuran was degassed in a nitrogen stream and in the same manner as in Example P-401 for 12 hours shine.

The resulting reaction mixture was added to one liter of methanol to precipitate the polymer. The precipitate was collected and dried. There were obtained 72 g of polymer (P-403) having Mw of 5.3 × 10 ⁴ .

Examples P-404 to P-416:

The procedures of Example P-402 were repeated except that instead of the macromonomer (M-401), the macro-monomers corresponding to the macromonomer segment (M _A ) given in Table 402 were used. The polymers (P-404) to (P-416) having Mw values in the range of 5 × 10 ⁴ to 8 × 10 ^{4 were} obtained. The Mw values of the macromonomers used are also given in Table 402.

Table 402

Examples P-417 to P-429:

The polymers listed in Table 403 were prepared in a similar manner to Example P-401. The poly mers (P-417) to (P-429) having Mw values in the range of 4 × 10 ⁴ to 8 × 10 ^{4 were} obtained. The Mw values of the monofunctional macromonomers corresponding to the units (M _B -17) to (M _B -29) used for the preparation ranged from 6 × 10 ³ to 9 × 10 ⁴ .

Table 403

Preparation Examples of the Polymer (Q) Example Q-1:

A solution of 95 g of 2-chlorophenyl methacrylate, 5 g of methacrylic acid and 200 g of toluene was heated to 90 ° C in a stream of nitrogen. 7.0 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto and reacted for 4 hours. Then another 2 g of AIBN was added and it was reacted for a further 2 hours. The weight average molecular weight (Mw) of the resulting polymer (polymer (Q-1)) was 7.7 × 10 ³ .

Example Q-2:

A solution of 96 g of 2,6-dichlorophenyl methacrylate, 5 g of acrylic acid, 2 g of n-dodecyl mercaptan and 200 g of toluene was heated to 75 ° C in a stream of nitrogen. Then 1 g Azobisisobu tyronitrile (AIBN) was added and carried out for 4 hours. Subsequently, another 0.5 g of AIBN was added, followed by further reaction for 3 hours. After cooling, the reaction mixture was precipitated in 2 L of a methanol / water (9/1) mixture, and the precipitate was separated by decantation and dried under reduced pressure. There were obtained 78 g of a wax-like polymer (Q-2) (Mw: 6.0 × 10 ³ ).

Examples Q-3 through Q-16:

The polymers (Q-3) to (Q-16) shown in Table 2 were used in a similar manner as in Example Q-1.

Table 2

Example Q-17:

A solution of 100 g of benzyl methacrylate, 4 g of thiosalicylic acid, 160 g of toluene and 40 g of ethanol was heated to 75 ° C in a nitrogen stream and then 1.0 g of 2,2'-azobisisobutyronitrile (AIBN) was added and it became a 4-hour implementation carried out. Subsequently, another 0.4 g of AIBN was added and followed by a further 2 hours of reaction. Subsequently, another 0.2 g of AIBN was added, followed by reaction for a further 3 hours. The weight average molecular weight Mw of the resulting polymer (polymer (Q-17)) was 6.8 × 10 ³

Examples Q-18 through Q-27:

The procedures of Example Q-17 were repeated except that instead of 100 g of benzyl methacrylate and 4 g of thiosalicylic acid, the methacrylates and mercapto compounds listed in Table 3 were used. The Mw values of the resulting polymers (Q-18) to (Q-27) ranged from 5 × 10 ³ to 8 × 10 ³ .

Table 3

Examples Q-28 through Q-35:

A solution of the monomers shown in Table 4 (total weight 100 g), of 3 g of thiosalicylic acid, 160 g of toluene and 40 g of methanol was heated to 60 ° C with stirring in a nitrogen stream. To this was added 2 g of azobisisovaleronitrile (AIVN) and then reacted for 4 hours. Thereupon, another 0.8 g of AIVN was added, followed by reaction for a further 4 hours. The weight average molecular weight of the resulting polymers (Q-28) to (Q-35) ranged from 5 × 10 ³ to 8 × 10 ³ .

Example Q-36:

A solution of 99.5 g of 1-naphthyl methacrylate, 0.5 g of methacrylic acid, 150 g of toluene and 50 isopropanol was heated to 80 ° C in a stream of nitrogen. 5.0 g of 4,4'-azobis (4-cyanogen) valeric acid (ACV) was added thereto and the reaction mixture was stirred for 5 hours. Then another gram of ACV was added and stirring was continued for a further 3 hours. The weight average molecular weight (Mw) of the resulting polymer (Q-36) was 7.5 × 10 ³ .

Example Q-37:

A solution of 50 g of methyl methacrylate and 150 g of methylene chloride was cooled to -20 ° C in a stream of nitrogen. A previously prepared 10% solution of 1,1-diphenyl hexyllithium in hexane (1.0 g) was added thereto followed by stirring for 5 hours. Subsequently, carbon dioxide was bubbled at a flow rate of 10 ml / cm ³ with stirring for 10 minutes. Thereafter, the cooling was stopped and the reaction mixture was allowed to come to room temperature with stirring. Thereafter, the reaction mixture was added to a solution of 50 ml of 1N hydrochloric acid in one liter of methanol to precipitate the polymer, whereupon the resulting white powder was collected. The powder was washed with water until the washings were neutral and dried in vacuo. The yield of resulting polymer (Q-37) was 18 g, the Mw value thereof was 6.5 × 10 ³ .

Example Q-38:

A solution of 96 g of benzyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to 75 ° C in a stream of nitrogen. 1.0 g of ACV was added and the reaction was carried out for 6 hours. Subsequently, another 0.4 g of ACV was added, followed by reaction for a further 3 hours. The weight-average molecular weight Mw of the resulting polymer (Q-38) was 7.8 × 10 ³ .

Example Q-39:

A solution of 100 g of benzyl methacrylate and 200 g of tetrahydro Furan was sufficiently degassed in a nitrogen stream and cooled to -78 ° C. There were 3.2 g of 1,1-diphenylbutyllithium added, followed by a 12-hour implementation. Dar Subsequently, a solution of 60 g was added to the resulting mixture Methyl methacrylate, 6 g of triphenylmethyl methacrylate and 5 g Tetrahydrofuran, which previously degassed in a nitrogen stream was added in sufficient quantity, whereupon an 8- hourly implementation took place. After cooling the mixture at 0 ° C, 10 ml of methanol were added and the reaction was continued for 30 minutes. Then the polymerisa tion canceled. The resulting polymer solution was left come to 30 ° C with stirring, whereupon 3 ml of a 30% Lö solution of hydrochloric acid in ethanol. It was then stirred for an hour, whereupon the resulting Mix under reduced pressure to half the amount  was evaporated and then added to a liter of petroleum ether was to precipitate the resulting polymer.

The resulting precipitate was collected and dried under reduced pressure. The yield of the resulting polymer (Q-39) was 72 g, the Mw value thereof was 9 × 10 ³ .

Example Q-40:

A solution of 70 g of methyl methacrylate, 30 g of methyl acrylate, 3.5 g of (tetraphenylporphinate) aluminum methyl and 80 g of methylene chloride was brought to 30 ° C. The resulting reaction mixture was irradiated from a distance of 25 cm through a glass filter with light from a 300 W xenon lamp and reacted for 30 hours. Then, 60 g of methyl acrylate and 3.2 g of benzyl methacrylate were added and the reaction mixture was irradiated in the same manner for another 8 hours. Then, 3 g of methanol were added to the reaction mixture. The reaction mixture was stirred for 30 minutes, whereupon the reaction was stopped. Subsequently, Pd-C was added and the resulting mixture was catalytically reduced at 25 ° C for 1 hour. The resulting mixture was added to 500 ml of petroleum ether to precipitate the resulting polymer, whereupon the insoluble material was collected by filtration, reprecipitated in 500 ml of petroleum ether, and then collected by filtration and dried. The yield of resulting polymer (Q-40) was 95 g, the Mw value thereof was 9.5 × 10 ³ .

EXAMPLE Q-41

A solution of 100 g of phenyl methacrylate and 200 g of toluene was added sufficiently degassed in a stream of nitrogen and to -78 ° C. cooled. There were 5.0 g of 1,1-diphenyl-3-methylpentyllithium was added and then was an implementation for 8 hours carried out. Then, the resulting mixture became a Solution of 60 g of benzyl methacrylate and 4.6 g of 4-vinylphenoxy trimethylsilane, followed by stirring for 8 hours. to closing 3 g of methanol were added and it was more Stirred for 30 minutes.

Then, 10 g of a 30% solution of hydrochloric acid in ethanol was added and the resulting mixture was stirred at 25 ° C for 1 hour before being added to 1 liter of methanol to precipitate the resulting polymer. The resulting precipitate was collected, washed twice with 300 ml of methanol and dried. The yield of the resulting polymer (Q-41) was 100 g, the Mw value thereof was 1.0 × 10 ⁴ .

EXAMPLE Q-42

A mixture of 67 g of 2-chlorophenyl methacrylate and 9.6 g of benzyl N, N-diethyldithiocarbamate was placed in a vessel in a stream of nitrogen and sealed, heated to 50 ° C and then exposed to light at a distance of 10 cm for 8 hours exposed by a 400 W high pressure mercury vapor lamp through a glass filter to perform photopolymerization. To the resulting reaction mixture was added 32 g of methyl acrylate, 1 g of acrylic acid and 180 g of methyl ethyl ketone. Thereafter, the vessel was purged with nitrogen, and the irradiation was continued for 10 hours. The resulting reaction mixture was added to one liter of a 3/4 volume ratio hexane / ethanol solution to precipitate the resulting polymer, and then the precipitate was collected and dried. The yield of the resulting polymer (Q-42) was 73 g, the Mw value thereof was 8 × 10 ³ .

EXAMPLE Q-43

A mixture of 75 g of 2,6-dichlorophenyl methacrylate and 6.5 g of benzyl isopropylxanthate and 150 g of tetrahydrofuran was placed in a vessel in a stream of nitrogen and sealed and then heated to 50 ° C. Then, the mixture was irradiated from a distance of 10 cm for 8 hours with light from a 400 W high-pressure mercury vapor lamp through a glass filter to perform photopolymerization. Then, 22 g of methyl acrylate was added, followed by purging the vessel with nitrogen and continuing the irradiation for 10 hours. Then, 3 g of 2- (2'-carboxyethyl) carbonyl oxyethyl methacrylate was added, the vessel was rinsed with nitrogen again, and the irradiation was continued for another 8 hours. The resulting mixture was added to 2 liters of methanol to precipitate the resulting polymer, which was collected in powder form and dried. The yield of resulting polymer (Q-43) was 63 g, the Mw value thereof was 8 × 10 ³ .

EXAMPLE Q-44

To a solution of 80 g of ethyl acrylate, 20 g of methacrylic acid, 5 g 2-merceptoethanol and 200 g of tetrahydrofuran were added with stirring heated to 60 ° C in a stream of nitrogen. Then 1.0 g 2,2'-azobisisovaleronitrile (A.I.V.N.) was added and it became Implemented for 4 hours. Thereupon, another 0.5 g A.I.V.N. added, followed by another 4 hour implementation took place.

The resulting reaction mixture was allowed to come to 20 ° C. Then, a solution of 22 g of 4,4'-azobis (cyanovaleric acid), 12 g of dicyclohexyldicarbodiimide, 0.2 g of 4- (N, N-dimethyl) pyridine and 30 g of tetrahydrofuran was added dropwise over 1 hour, and it became 2 Stirred for hours. Subsequently, 5 g of an 85% strength aqueous formic acid solution were added and the mixture was stirred for a further 30 minutes. After removal of the crystalline precipitate, the filtrate was evaporated under reduced pressure at 25 ° C to remove solvent. The weight-average molecular weight (Mw) of the resulting polymer (polymer initiator) was 3.5 × 10 ³ .

A solution of 70 g of 2-chloro-6-methylphenyl methacrylate and 170 g of toluene was heated to 85 ° C with stirring in a stream of nitrogen. 30 g of the above-obtained polymer initiator was dissolved in 30 g of toluene and purged with nitrogen, and the solution was added to the above solution and reacted for 8 hours. The resulting polymer was precipitated in 2 liters of methanol, collected as a powder and dried. The yield of the resulting polymer (Q-44) was 65 g, the Mw value thereof was 8 × 10 ³ .

EXAMPLES Q-45 TO Q-54

The polymers (Q-45) to (Q-54) shown in Table A were prepared in a similar manner as in Example Q-42. The weight-average molecular weight of the resulting poly mers ranged from 7 × 10 ³ to 9 × 10 ³ .

EXAMPLE Q-55

A mixture of 90 g of methyl acrylate, 10 g of acrylic acid and 26.8 g of initiator (I-10) having the formula given below was heated to 40 ° C in a stream of nitrogen. The resulting mixture was exposed from a distance of 10 cm for 10 hours with light from a 400 W high pressure mercury vapor lamp through a glass filter to perform photopolymerization. The resulting polymer was precipitated in 1 liter of methanol, whereupon the precipitate was collected and dried. The yield of the resulting polymer was 75 g, the weight average molecular weight as measured by GPC with a polystyrene standard (this method was also used for the following polymers (Q)) was 4 × 10 ³ .

40 g of polymer, 60 g of benzyl methacrylate and 100 g of tetrahydrofuran were heated to 50 ° C. in a stream of nitrogen. The irradiation was again carried out for 15 hours. The resulting polymer was precipitated in 1.5 L of methanol, whereupon the precipitate was collected and dried. The yield of the resulting polymer (Q-55) was 75 g, the Mw value thereof was 9 × 10 ³ .

EXAMPLE Q-56

The procedure of Example Q-55 was repeated except that the 26.8 g of initiator (I-10) was replaced by 43.6 g of initiator (I-11). The yield of the resulting polymer (Q-56) was 70 g, the Mw value thereof was 8.5 × 10 ³ .

EXAMPLE Q-57

A solution of 80 g of methyl methacrylate, 20 g of ethyl acrylate, 39.0 g of initiator (I-12) as indicated by the below Formula is shown, and 150 g of tetrahydrofuran was in heated to 50 ° C in a nitrogen stream. Thereupon became on the same way as in Example Q-39 an 8-hour Bestrah carried out.

The resulting polymer was precipitated in 1 liter of methanol, collected by filtration and dried. 60 g of the resulting polymer, 30 g of methyl methacrylate, 10 g of methacrylic acid and 100 g of tetrahydrofuran were heated to 50 ° C in a stream of nitrogen. Thereafter, irradiation was performed for 10 hours in the same manner as above. The resulting polymer was precipitated in 1 liter of methanol, collected and dried. There were obtained 6 g of polymer (Q-57) having a Mw of 1.2 × 10 ⁴ .

EXAMPLE Q-58

A solution of 50 g of methyl methacrylate and 100 g of tetrahydrofu ran was sufficiently degassed in a nitrogen stream and on Cooled to -78 ° C. Then, 7.2 g of 1,1-diphenylpentyllithium admitted and it was a 12-hour implementation durchge leads. Subsequently, a solution of 28 g of methyl acrylate, 6 g Triphenylmethylmethacrylat and 50 g of tetrahydrofuran, the had previously been sufficiently degassed in a stream of nitrogen, admitted, followed by an 8-hour implementation. Thereafter, a solution of 50 g of methyl methacrylate and 50 g tetrahydrofuran, which is sufficient in a stream of nitrogen was degassed, added to the above solution and thus 10 Implemented for hours.

The resulting mixture was allowed to come to 0 ° C and 10 ml of methanol was added followed by reaction for a further 30 minutes. Thereafter, the polymerization was terminated. The resulting polymer solution was allowed to come to 30 ° C with stirring and then 3 ml of a 30% hydrochloric acid solution in ethanol was added, followed by stirring for 1 hour. Then, the resulting mixture was evaporated to half under reduced pressure and then added to 1 liter of methanol to precipitate the resulting polymer. The precipitate was collected and dried under reduced pressure. The yield of the resulting polymer (Q-58) was 65 g, the Mw value thereof was 8 × 10 ³ .

EXAMPLE Q-59

A solution of 100 g phenyl methacrylate, 1.5 g (tetraphenyl porphinate) aluminum methyl and 200 g methylene chloride was heated to 30 ° C in a stream of nitrogen. The resulting reaction mixture was irradiated with light from a 300W xenon lamp through a glass filter from a distance of 25 cm for 12 hours. Thereafter, 40 g of ethyl acrylate and 9.2 g of benzyl methacrylate were added, and the reaction mixture was irradiated for a further 10 hours in the same manner as above. 100 g of phenyl methacrylate were then added and irradiation was continued for a further 12 hours. Then, 3 g of methanol was added to the reaction mixture, and it was stirred for 30 minutes, whereupon the reaction was stopped. Subsequently, Pd-C was added and the resulting mixture was catalytically reduced for 1 hour at 25 ° C. The resulting polymer was precipitated in 2 liters of methanol, whereupon the insoluble material was collected by filtration and dried. The yield of the resulting polymer (Q-59) was 160 g, the Mw value thereof was 9.5 × 10 ³ .

EXAMPLES Q-60 TO Q-69

The polymers (Q-60) to (Q-69) shown in Table B were prepared in a similar manner as in Example Q-56. The weight-average molecular weight of each of the polymers ranged from 8 × 10 ³ to 1 × 10 ⁴ .

EXAMPLES Q-70 TO Q-73

The procedure of Example Q-55 was repeated with the exception that instead of 26.8 g of the initiator (I-10) 1.5 × 10 ^-1 mol of one of the specified in Table C initiator were set. The resulting polymers had the same composition as the polymer (Q-55). The Mw values of the resulting polymers (Q-70) to (Q-73) ranged from 6 × 10 ³ to 9 × 10 ³ .

Table C

EXAMPLES Q-74 TO Q-80

A solution of 80 g of benzyl methacrylate, 20 g of acrylic acid and 22.6 g of initiator (I-17) was in a stream of nitrogen Heated to 40 ° C and in the same manner as in Example Q-39 5 Irradiated for hours. The resulting polymer was incorporated in 200 g of tetrahydrofuran dissolved, out in 1.0 liter of methanol falls, collected by filtration and dried.

A solution of 20 g of the above polymer, the monomer corresponding to the units given in Table D, and 100 g of tetrahydrofuran was irradiated for 15 hours in the same manner as explained above for a 30555 00070 552 001000280000000200012000285913044400040 0002004306047 00004 30436. The resulting polymer was precipitated in 1.5 liters of methanol, collected by filtration and dried. The Mw value of the resulting polymers (Q-74) to (Q-80) was in the range of 8 × 10 ³ to 1 × 10 ⁴ in a yield of 60 to 70 g.

EXAMPLE 1

A mixture of 1.5 g of metal-free phthalocyanine in the X- Form (available from DAINIPPON INK AND CHEMICALS INC.), 8.5 g polymer (R-1) as represented by the following formula is, 1.5 g of polymer (Q-5), 0.3 g of polymer (P-104) of the present ing invention, 0.15 g of compound A, as described by the fol ing formula, and 80 g of tetrahydrofuran was together with glass beads in a 500 ml glass container gege ben. The mixture was obtained with a paint shaker (available from TOYO SEIKI SEISAKUSHO) dispersed for 60 minutes and there The glass beads were then separated by filtration, to produce a dispersion for a photoconductive layer len.

The dispersion was applied to a paper base with a wire rod layer with a thickness of 0.2 mm, with the paper both an electrical conductivity treatment as well subjected to a treatment for solvent resistance had been. After the coating had been dried in air, until he was no longer sticky, he was in a convection oven Dried at 110 ° C for 20 seconds and then at 140 ° C for 1 hour heated to a photoconductive layer having a thickness of 8 microns to get.

The numbers of repeating units in the above Formula represents the weight ratio.

A thermoplastic resin solution having the following contents was made to form a transfer layer (or a removable transfer layer or a releasable layer) of the photoconductive layer.

Poly (vinyl acetate / crotonic acid) (95/5, Mw = 5 × 10⁴) | 3 g 28% aqueous ammonia 1 g ethanol 97 g

After the above solution with a wire rod on the photo conductive layer was applied, the coating became dried in an oven at 120 ° C for 20 seconds to a electrophotographic material for color proofing provide a transfer layer with a thickness of 1.3 microns had.

COMPARATIVE EXAMPLE A1

An electrophotographic material for color proofing was prepared in the same manner as in Example 1, with the Exception that 0.3 g of a random copolymer (RP-1) instead of 0.3 g of polymer (P-104) were used.

COMPARATIVE EXAMPLE B1

In the same manner as in Example 1, an electrophoto graphic material for color proofing, with the Except that 10 g of polymer (R-1) instead of 8.5 g of polymer (R-1) and 1.5 g of polymer (Q-1) were used.

TEST EXAMPLE

The electrostatic properties, transfer properties and image reproduction properties of the electrophotographic Color proofing materials used in Example 1 and in Comparative Examples A1 and B1 were obtained were beur Splits. The results are summarized in the following Table 5 quantity handled.  

Table 5

The properties shown in Table 5 became as follows assessed.

1) Electrostatic properties

Each of the electrophotographic materials was subjected to corona discharge for 20 seconds at -6kV in a dark room at 20 ° C. (65% relative humidity) by means of a paper analyzer (Paper Analyzer SP-428, Kawaguchi Electric Co., Ltd.), and then Leave for 10 seconds, whereupon the surface potential (V ₁₀ ) was determined. Thereafter, the material was left in the dark for a further 120 seconds, and then the potential (V ₁₃₀ ) was again determined to obtain a percent dark decay retention rate (DRR), ie, a potential retention rate after 120 seconds of decay in the dark calculated according to the following equation:

DRR (%) = (V ₁₃₀ / V ₁₀ ) × 100.

Further, the surface of the photoconductive layer which was in contact with the transfer layer was charged to -500 V by a corona discharge, whereupon the material was irradiated with 780 nm wavelength monochromatic light and the time measured for a 1 / 10 decrease in surface potential (V ₁₀ ) was required. On the basis of the time obtained, the exposure (E _1/10 ) in erg / cm ^{2 was} calculated.

The above properties were also at a temperature of 30 ° C and a relative humidity of 80 ° C determined. The following conditions are 20 ° C, 65% relative air humidity and 30 ° C, 80% relative humidity as Be conditions I and II respectively.

2) transmission characteristics

A sheet of coated paper was printed on an electrophoto graphic material placed with a transfer layer and then at a speed of 5 mm / sec between two Hollow heat rollers made of metal with a silicone rubber layer were coated and inside an infrared lamp Heizvorrich contained, transported therethrough.

The surface temperatures of the rolls, upper and lower, were kept at 120 ° C, the rolls were arranged to give a nip pressure of 5 kgf / cm ² , and the belt speed was regulated to 5 mm / sec.

After cooling to room temperature, it was coated paper lay on the material, the paper from the electropho detached tographic material. The quality of the be layered paper transferred image was by visual inspection assessed.

3) Image reproduction properties

On each of the electrophotographic materials was under the conditions (I) or (II) generates an image and then became the image reproduction property of the color control judged after the transfer.

Each of the electrophotographic materials was charged in the dark by corona discharge to +450V. The charged electrophotographic material was imagewise exposed with a Ga-Al-As semiconductor laser (oscillation wavelength 780 nm) with an output power of 5 mW. An exposure of 30 erg / cm ^{3 was} measured on the electrophotographic material. The exposure was carried out at a pitch of 25 μm at a scanning speed of 300 cm / sec in a negative mirror image manner on the basis of the information on the color yellow among the information on yellow, magenta, cyan and black on a hard disk of a Color scanning system were recorded as digital image data and were obtained by reading an original using the color scanning system and performing a color separation and correction for some system-specific color reproductions. Subsequently, the exposed electrophotographic material was coated with a yellow liquid developer for a signature system (available from Eastman Kodak) diluted by 75 times by weight with Isopar H (available from Esso Standard Oil Co.) Development device developed with reversal. The processor had two planar development electrodes and the bias was +400 V to electrically deposit the toner on the exposed areas of the electrophotographic material. Thereafter, the developed electrophotographic material was rinsed in an Isopar H bath to remove contamination in the non-image area.

The above procedure was performed using the information for Magenta, Cyan, and Black instead of Yellow's Information repeated.

That on the electrophotographic material after the picture The existing image was created using a heating system fixed roller.

Then, a coated paper (plain print paper) was placed on the fixed image electrophotographic material and then passed at a speed of 10 mm / sec between two rubber rollers which were in contact under a pressure of 15 kgf / cm ² and whose surface had a surface constant temperature of 120 ° C had. After cooling to room temperature, the coated paper was peeled from the electrophotographic material. The image formed on the coated paper was visually evaluated for fog and image quality.

As shown in Table 5, the materials of Example 1 (according to the invention) and Comparative Example A1 independently of the variation of the conditions good electrostatic properties companies.

However, the electrostatic properties, particularly the dark decay retention rate (DRR) and photosensitivity (E _1/10 ) of the material obtained in Comparative Example B1, which included only the conventional polymer as the binder resin, were very poor.

It is assumed that the above difference is based on that in the electrophotographic material of the present invention for the color proof the polymer (Q) the photoconductive Ver Bond sufficiently adsorbed and a uniform Disper allows the photoconductive compound and thereby Ensures a condition that is adequate and equal moderate interaction between the chemical sensitizer, the compound (A) and the photoconductive compound made possible light.

Next, the transfer layers of Example 1 and Comparative Example B1, which is the polymer (Q) of the before underlying invention, materials obtained vollstän dig transmitted to the receiving materials while the mate rial of Comparative Example A1 unsuccessful from the be layered paper could be peeled off, but the over tragungsschicht or photoconductive layer thereof was damaged.

It is assumed that the above difference is based on that in the electrophotographic material of the invention and the material of Comparative Example B1, the polymer (P), wel This is the fluorine-containing copolymer in which photoconductive Layer migrates and at the time of formation of the photoconductive concentrated layer on the surface of the layer and then a cured film by a crosslinking agent forms by chemical bonds between the polymer chains, to create a clear interface of the layers while such a clear interface in the material of Vergleichbei play A1, which is a conventional statistical copolyme operated, not formed.

In addition, the inventive electrophotographic Material the color control deduction independently of the change of  Provide environmental conditions with good image quality while the material of Comparative Example A1 is not satisfactory could provide the picture because of the transmission characteristics same bad, and the material of Vergleichbei play B1 to extremely poor playback characteristics high humidity conditions.

Further, the peel properties of the photoconductive Layers that in Example 1 and Comparative Example A1 gebil det were examined by checking the adhesion of this photo conductive layers according to JIS Z 0237-1980 (adhesive tape or arc test method) prior to the formation of the transfer layer certain. As a result, liabilities of the photoconductive 6 p layer for the material of Example 1 and 330 p for the material of Comparative Example A1.

As described above, only the electrophotographic Material of the present invention has excellent properties th.

EXAMPLE 2

A mixture of 200 g of photoconductive zinc oxide, 10 g of polymer (Q-1), 40 g of polymer (R-2) represented by the following formula, 8 g of polymer (P-103) of the present invention, 0.018 g Dye (D-1) represented by the following formula, 0.20 g of N-hydroxysuccinimide and 300 g of toluene were placed in a homogenizer (Nihon Seiki Co., Ltd.) and at 9 x 10 ³ rpm for 10 minutes dispersed.

To this dispersion, 0.3 g of phthalic anhydride and 0.01 g of o-chlorophenol were added and dispersed at 1 × 10 ³ rpm for 1 minute.

The dispersion was placed on a base with a wire rod a paper backing with a thickness of 0.2 mm, both an electrical conductivity treatment as well as a  Had been subjected to solvent resistance treatment, applied. After the coating has been dried in air was until he was tack-free, he was in one for 1 hour Air-circulating oven dried at 90 ° C to give a photosensitive To obtain layer with a thickness of 10 microns.

The same thermoplastic resin solution as in Example 1 was prepared, applied to the photosensitive layer and dried to an over on the photosensitive layer to form a transfer layer.

COMPARATIVE EXAMPLE C1

In the same manner as in Example 2, an electrophoto graphic material for color proofing, with the Except that instead of 10 g of polymer (Q-1) and 40 g of poly Mer (R-2) 50 g of polymer (R-2) were used alone.  

TEST EXAMPLE

Smoothness, electrostatic properties, over and the image reproduction properties of the Materia obtained in Example 2 and Comparative Example C1 were assessed. The results are shown in Table 6 below summarized.

Table 6

The electrostatic properties given in Table 6 and transmission characteristics were in the same way as judged in Example 1 while the smoothness and the image reproduction properties were evaluated as follows.  

1) Smoothness of the photoconductive layer

The smoothness of the electrophotographic material (sec / cm ³ ) was determined with a Beck smoothness tester (Kumagaya Rikoh Co., Ltd.) under the condition of 1 cm ³ air volume.

2) image reproduction properties

Each of the electrophotographic materials was charged in the dark by corona discharge to -600V. The charged electrophotographic material was imagewise exposed by means of a semiconductor laser (oscillation wavelength 780 nm) with 25 erg / cm ³ irradiation, measured on the surface of the electrophotographic material, in a positive mirror image manner, based on the information on the color Yellow. The residual potential on the exposed areas was -120 V. Thereafter, the exposed electrophotographic material was diluted with 50 times the amount of Isopar H using a yellow toner for VERSATECK 3000 (electrostatic color plotter, available from Xerox Co.). using a developing device having two planar developing electrodes, using a bias voltage of -200 V to electrically deposit the toner on the unexposed areas of the electrophotographic material, and then developing the developed electrophotographic material in an Isopar H- Bath flushed to remove background contamination in the non-image areas.

The above procedure was performed using the information from respectively magenta, cyan and black instead of the information for Yellow repeated.

Subsequently, coated paper was put on the electrophotographic material developed with the four color toners, and then transported at a speed of 6 mm / sec through two rubber rollers which were in contact under a pressure of 10 kp / cm ³ and their surfaces kept constant at 120 ° C were held.

After cooling to room temperature, the coated paper became separated from the electrophotographic material.

As shown in Table 6, the material of Example 2 showed (According to the invention) extremely excellent electrostatic egg characteristics and when the ambient conditions changed, the fluctuation of these properties was not significant. Furthermore, in practical imaging with this material according to the invention good image reproduction properties in terms of fine images, such. B. fine lines and finer Printed characters, obtained without background contamination. Ande On the other hand, the electrostatic properties of the in Comparative Example C1 obtained extremely poor, especially under high humidity, and one in practice acceptable image reproduction was made with this comparison material not received. That is, veil on the non-image and image density were unsatisfactory and that Disappearance of fine lines was noticeable.

Both materials have good transmission properties obtained and it was found that the peel properties of the photoconductive layer by the polymer (P) not only in the photoconductive layer containing the organic photoconduct contains capable connection, but also in the layer that containing the inorganic photoconductive compound, verbes can be sert.

Further, the peel properties of the photoconductive Layers that in Example 2 and Comparative Example C1 herge were determined by checking the adhesion of this photo conductive layers according to JIS Z 0237-1980 (adhesive tape or sheet test method) before the formation of the transfer layer examined. As a result, liabilities of the photoconductive  layer of 8 p for the material of Example 102 and of 380 p for the material of Comparative Example C1.

As described above, the electrophotographic material al for the color proof of Example 2 regardless of the Umge conditions good transmission properties and good picture reproducing properties.

EXAMPLE 3

5 g of 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane as organic photoconductive compound, 1 g of polymer (Q-32), 3 g polymer (R-3) represented by the following formula 0.8 g of polymer (P-119) of the present invention, 40 mg Dye (D-2) represented by the following formula and 0.20 g of an anilide compound (B) produced by the represented by the following formula as a chemical sensitization were in a mixture of 30 ml of methylene chloride and 30 Dissolved methylene chloride to a solution for a photoconductive to form a layer.

The solution was coated on an electrically conductive transparent support comprising a polyethylene terephthalate support (100 μm in thickness) with an indium oxide film deposited thereon and having a surface resistance of 10 ³ Ω by means of a wire-wound rod to form a photoconductive layer having a thickness wear of about 4 microns.

The in an adhesion test with a tape, on the back Adhesive, which was carried out to the teilwei the presence of the polymer (P) on the surface of the photo conductive layer to confirm, results obtained showed that the adhesion of the photoconductive layer of the material according to the invention in comparison with a photoconductor capable layer in the same way as in Example 3 was prepared, with the exception that instead of the polyme (P-119) the polymer (R-3) used in the same amount became one seventieth.

The same thermoplastic resin solution as in Example 1 was prepared, applied to the photoconductive layer and dried to a transfer layer on the photoconductive gene layer to produce.

A tape with adhesive on the back was on the top surface of the removable layer attached and subtracted. When Only the transfer layer was slightly removed from the result photoconductive layer separated.  

The picture quality and the transmission characteristics of the so obtained electrophotographic material were applied to the same as in Example 1, except that a He-Ne laser with an oscillation wavelength of 630 nm instead of the semiconductor laser with an oscillation wavelength ge of 780 nm was used.

After transfer to coated paper became a clear Color image obtained without veil. The picture had one sufficient strength.

EXAMPLE 4

A mixture of 5 g of Bisazo pigment, by the following Formula is shown, 95 g of tetrahydrofuran, 1.5 g of polymer (Q-17) and a solution of 3.5 g polyester resin, Byron 200 (available from TOYOBO CO., LTD.) in 30 g of tetrahydrofuran was sufficiently ground in a ball mill. thereupon The mixture was pulled and 520 g were added with stirring Added tetrahydrofuran. The resulting dispersion was washed with a wire wound rod on the same electrically leiti transparent support as described in Example 1, around a charge generating layer with a thickness of 0.7 μm to build.

Thereupon, a solution of 20 g of hydrazone compound was added represented by the following formula, 2 g of polymer (P 102), 20 g of polycarbonate resin (Lexan 121, available from Gene Ral Electric Co.), 0.04 g of isophorone diisocyanate, 0.001 g of Te Trabutoxytitanat and 160 g of tetrahydrofuran with a wire wrapped rod applied to the charge generating layer dried at 60 ° C for 30 seconds and 1 hour at 120 ° C. heated to a charge-transporting layer with a Thickness of about 18 microns produce. Thus, the obtained electrophotographic material two functional layers, d. H. a charge generating layer and a charge transport layer, on.

The same thermoplastic resin solution as in Example 1 was prepared, applied to the photoconductive layer and dried to form a transfer on the photoconductive layer forming layer.

A tape with adhesive on the back was on the top surface of the transfer layer attached and subtracted. When  The result was only the transfer layer of the photoconductive layer separated.

The picture quality and the transmission characteristics of the so obtained electrophotographic material were applied to the same as in Example 1, except that a He-Ne laser with an oscillation wavelength of 630 nm instead of the semiconductor laser with an oscillation wavelength ge of 780 nm was used.

After transfer, on the coated paper a clear color copy without veil. The picture had sufficient strength.

EXAMPLES 5 to 7

Electrophotographic materials for the color proof were prepared in the same manner as in Example 1, with the Except that 0.3 g of polymer (P), as shown in the following table 7, instead of 0.3 g of polymer (P-104) used were.

The electrostatic properties, transfer properties and image rendering properties of the resulting electropho tographic materials were processed in the same way as in Example 1 assessed. The results are summarized in Table 7 quantity handled.  

Table 7

As can be seen from Table 7, all materials showed the Examples 5 to 7 good electrostatic properties, About tragungsseigenschaften and image reproduction properties, the those of the material of Example 1 were comparable.

The adhesive strength of each of the materials of example 5 to 7 was in the range of 5 to 8 p, d. h., these materials showed good peel properties.

The electrophotographic material, in the same way as prepared in Example 1, with the exception that the Polymer (R-1) instead of the polymer (P-104) in the same Quantity was used, showed worse transmission companies, d. h., The photoconductive layer of this material could not successfully deducted from the transfer layer become.  

The electrophotographic materials for color proofing were prepared in the same manner as in Example 1, with with the exception that 10 g of polymer (R-1) instead of 8.5 g of poly Mer (R-1) and 1.5 g of polymer (Q-5) were used and that each of the polymers (P) described in Examples 5 to 7 ver were used instead of polymer (P-104) was used. The electrostatic properties of the resulting elek trophotographic materials deteriorated extremely, when the environmental conditions changed, especially at high temperature and high humidity, and with this mate rials were unable to reproduce images that were acceptable in practice gift properties are obtained. That is, the veil in the non-image areas and the image density were poor and the disappearance of fine lines and fine print marks became a noticeable problem.

Accordingly, the results of the above test examples show that the electrophotographic materials of the present invention deliver extremely satisfactory color control prints.

EXAMPLES 8 TO 27

In the same manner as in Example 1, electrophotographic made of phobic materials for the Farbandruck, with the Except that 1.5 g of polymer (Q), as described in the following Ta 8, instead of 1.5 g of polymer (Q-5) were det.

Table 8

The picture quality and the transmission characteristics of each of the electrophotographic materials thus obtained judged in the dark in the same manner as in Example 1. After transfer, clear on coated paper Preserved color copies without contamination of the background. The pictures had sufficient strength.

EXAMPLES 28 TO 50

In the same manner as in Example 1, electrophotographic made of phobic materials for the Farbandruck, with the Except that 1.5 g of polymer (Q), 0.3 g of polymer (P) and Vernet cationic compounds as shown in Table 9 below are, instead of 1.5 g of polymer (Q-5), 0.5 g of polymer (P-104) and the crosslinking compound used in Example 1 were set.

Table 9

The picture quality and the transmission characteristics of each of the electrophotographic materials thus obtained evaluated in the same manner as in Example 1.

After transfer, clear on coated paper Preserved color copies without contamination of the background. The pictures had sufficient strength.

EXAMPLES 51 TO 58

In the same manner as in Example 1, electrophotographic made of phobic materials for the Farbandruck, with the Except that 2 g of polymer (Q), 9 g of polymer (R) and 0.3 g of poly (P), as indicated in the following Table 10 used were.  

Table 10

The polymers (R-4) to (R-8) can be replaced by the following For be represented:

In the same manner as in Example 1, the above he holding photoconductive layers transfer layers formed to electrophotographic materials for the Far to obtain band pressure. When using these materials for Color proofs were clear picture copies without pollution of the background.

EXAMPLES 59 TO 66

In the same manner as in Example 1, electrophotographic made of phobic materials for the Farbandruck, with the Except that listed in Table 11 below Polymers and solvents instead of poly (vinyl acetate / cro Tonsäure) were used.

Table 11

The electrostatic properties, transfer properties and image reproducing properties of the obtained materials were examined in the same manner as in Example 1. All Materials showed similar properties in this respect like the material of Example 1.

Claims (13)

Anspruch [en] An electrophotographic material for color proof which can be used in a process for producing color control prints in which at least one color toner image is electrophotographically printed on a transfer layer and then transferred to a sheet material together with this transfer layer, and one Layer support, a photoconductive layer and a transfer layer in this order, characterized in that the photoconductive layer comprises a polymer (P) selected from the group consisting of the following polymers (P ₁ ), (P ₂ ), (P ₃ ) and ( P ₄ ), a polymer (Q) selected from the following polymers (Q ₁ ) and (Q ₂ ), and a polymer (R) containing at least one unit with one or more light and / or or thermosetting groups contains; the polymer (P) is present at least in the region near the surface indicative of the transfer layer; and that the surface of the photoconductive layer in contact with the transfer layer has an adhesive strength of not more than 150 p as measured by the test of JIS Z 0237/1980;
Polymer (P ₁ ):
linear block copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one polymer segment (Y) containing units having one or more light and / or thermosetting Grup contains pen, comprises;
Polymer (P ₂ ):
star-shaped copolymer containing at least three type AB block copolymer chains consisting of a polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s) and a polymer segment (Y) containing units having one or more light and / or thermosetting groups, said block copolymer chains being linked together by an organic group (Z);
Polymer (P ₃ ):
A graft copolymer containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s), and at least one polymer segment (Y) containing units having one or more light and / or thermosetting groups includes;
Polymer (P ₄ ):
A block copolymer of AB or ABA type containing at least one polymer segment (X) containing not less than 50% by weight of units containing fluorine atom (s) and / or silicon atom (s) and at least one polymer segment (Y) A unit containing one or more light and / or heat curing groups comprises, wherein at least one of these polymer segments (X) is the following polymer segment (X ') of the graft type, at least one of Polymerseg elements (Y) the following polymer segment (Y ') is of the graft type, or at least one of the polymer segments (X) the following polymer segment (X') of the graft type and we least one of the polymer segments (Y) the following polymer segment (Y ') of the graft type is:
Graft type polymer segment (X '): polymer segment having a weight average molecular weight of from 1 × 10 ³ to 2 × 10 ⁴ and containing at least one macromonomer segment (M _A ) containing not less than 50% by weight of units containing fluorine atom ( en) and / or silicon atom (s);
Polymer segment (Y ') graft type: polymeric segment having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ comprising at least one macromonomer (M _B) which has no units having fluorine atom (s) and / or silicon atom ( en) includes;
Polymer (Q ₁ ):
A homopolymer or random copolymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing not less than 30% by weight of units represented by the following formula (I): -CH (a ₁ ) -C (a ₂ ) (COOR ₃ ) - (I) wherein a ₁ and a ₂ each independently represent hydrogen, halogen, cyano or a hydrocarbon group, R _{3 represents} a hydrocarbon group; and at least one polar group selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, -PO (OH) (R ₁ ), wherein R _{1 represents} a hydrocarbon group or -OR ₂ (R ₂ = hydrocarbyl group of substances), and residues of cyclic anhydrides; Polymer (Q ₂ ):
linear block copolymer having a weight-average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing at least one segment (M) containing not less than 30% by weight of units of the above formula (I); at least one segment (N) having at least one polar group selected from -PO ₃ H ₂ , -SO ₃ H, -COOH, - PO (OH) (R ₁ ), wherein R _{1 is} a hydrocarbon group and -OR ₂ (R ₂ = hydrocarbon group), and residues of cyclic anhydrides. 2. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₁ ) and the polymer (Q) is the polymer (Q ₁ ). 3. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₂ ) and the polymer (Q) is the polymer (Q ₁ ). 4. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₃ ) and the polymer (Q) is the polymer (Q ₁ ). 5. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₄ ) and the polymer (Q) is the polymer (Q ₁ ). 6. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₁ ) and the polymer (Q) is the polymer (Q ₂ ). 7. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₂ ) and the polymer (Q) is the polymer (Q ₂ ). 8. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₃ ) and the polymer (Q) is the polymer (Q ₂ ). 9. An electrophotographic material according to claim 1, characterized in that the polymer (P) is the polymer (P ₄ ) and the polymer (Q) is the polymer (Q ₂ ). 10. An electrophotographic material according to any one of preceding claims, characterized in that the Polymer (P) in a layer in contact with the Transfer layer is in an amount of 1 to 30 wt .-%, based on the total weight of the layer before is present. 11. An electrophotographic material according to any one of preceding claims, characterized in that the Polymer (Q) in a layer containing the photoconductive Compound contains, in an amount of 1 to 100 parts by weight Parts per 100 parts by weight of the photoconductive compound is included. 12. An electrophotographic material according to any one of preceding claims, characterized in that the Polymer (R) in a layer in contact with the  Transfer layer is in an amount of 5 to 99.1 wt .-%, based on the total weight of the layer before is present. 13. Method for producing a color control print, in the at least one color toner image electrophotographically on an electrophotographic material for color printing, which a substrate, a photoconductive hige layer and a transfer layer in the angege enclosed sequence is formed, and then along with the transfer layer on a sheetmate transferred to the color control print characterized in that the photoconductive Layer of the electrophotographic material as in is defined in any one of claims 1 to 12.