United States Patent (11) 3,617,288

72 Inventors Richard B. Hartman (5ll Int. Cli........................................................ G03c 1/60,

White Bear Lake; GO3c 1172
George H. Smith, Maplewood, both of 50) Field of Search............................................ 96/90, 88,
Minn.
21 Appl. No. 857,552 48, 115 P., 35.1, 73,74, 65, 66.3,99, 100, 1.3, 1.5
22) Filed Sept. 12, 1969 (56) References Cited
45) Patented Nov. 2, 1971 UNITED STATES PATENTS
73 Assignee Minnesota Mining and Manufacturing 3,081,165 3/1963 Ebert............................ 96/1.3
Company
Saint Paul, Minn. 3,374,094 3, 1968 Wainer......................... 96/90X
Primary Examiner-John T. Goolkasian
Assistant Examiner-M. E. McCannish
Attorney-Kinney, Alexander, Sell, Steldt & De La Hunt
54) PROPENONE SENSTIZERS FOR THE
PHOTOLYSS OF ORGANIC HALOGEN
COMPOUNDS ABSTRACT: Photosensitive compositions containing non
8 Claims, No Drawings basic propenone compounds as sensitizers for photolyzable
52 U.S.C.......................................................
organic halogen compounds, and image recording elements in
96/90, which at least one layer contains such photosensitive composi
96/88 tions.
 3,617,288
2
PROPENONE SENSITIZERS FOR THE PHOTOLYSIS OF heterocyclic radical. The various radicals comprising the
ORGANIC HALOGENCOMPOUNDS propenone may be substituted or unsubstituted, provided the
This invention relates to a new class of sensitizers for the resulting compound is free of amine groups more basic than
photolysis of organic halogen compounds. In particular this in the diphenylamino radical. R is desirably free of electron
vention relates to sensitizers which extend the photolysis of or withdrawing groups, such as nitro, azo, etc., but may contain
ganic halogen compounds to higher wavelengths of light. releasing groups such as alkyl, aryl, ether, thioether, halogen,
Organic halogen compounds are widely used in the graphic etc. or secondary aromatic amino groups. Propenones in
arts field to produce commercially useful photosensitive con which n=2 may be prepared from the Claisen condensation of
structions. They may be used as photoinitiators for free radical 10 p-diphenylaminocinnamaldehyde with ketones containing an
adjacent methyl or methylene group. Propenones in which
photography (e.g. printout and bleach systems),
photopolymerization, and photoinduced acid catalyzed reac n=1 may be prepared from the base catalyzed Claisen conden
tions of many types. Various photosensitive products useful in sation of p-diphenylaminobenzaldehyde with ketones having
printing, duplicating, copying and other imaging systems can an adjacent methyl or methylene group to give a 1-substituted
be prepared with such organic halogen compounds. 15 3-(p-di-phenylaminophenyl)2-propene-1-one. The
Organic halogen compounds are known to photodissociate propenones are dyes containing no readily available unshared
to give free radical halogen, such as free radical bromine and electrons and hence are stable in the presence of base sensi
chlorine, which are good hydrogen abstractors and which will tive materials. Such propeones are known in the literature, see
produce acid in the presence of hydrogen donors. Their use in Belgian Pat. No. 710,239.
photopolymerization processes is described in Light Sensitive 20 Photolyzable organic halogen compounds capable of
Systems: Chemistry and Application of Nonsilver Halide Photo generating free radical halogen under the influence of light are
graphic Processes, J. Kosar, J. Wiley & Sons (New York, known. Preferred photolyzable organic halogen compounds
1965), pages 180-181. Both the free radical halogen and the are nongaseous (i.e. solid or liquid) at room temperature and
photoproduced acid have been used in various systems involv have a polarographic half wave reduction potential above
ing the photochemical formation and destruction of dyes, see 25 about -0.9. Illustrative are hexabromoethane, tetrabromo-o-
the above Kosar citation, pages 361-370. xylene, dibromotetrachloroethane, tribromotrichloroethane,
The use of sensitizers to broaden the spectral response of pentabromo-ethane, dibromocyanoacetamide, tris
organic halogen compounds is known, and yellow azo dyes, tribromomethyltriazine, dibromodibenzoylmethane,
styryl and leuco dye bases, and cyanine dyes are suitable for triiodomethane, tetrabromodifluoro-ethane, tribromoquinal
this purpose. Unfortunately most of such sensitizers cause 0 dine, hexachloro-p-xylene, etc.
serious stability problems under normal storage conditions The enhanced sensitivity of the photolyzable organic
prior to the use of the photosensitive sheet or film. Many of halogen compounds is not restricted to any particular use,
these known sensitizers contain a basic group, such as type of construction or imaging process. When coated onto a
dimethylamino, which chemically reacts with the organic 35 substrate with acrylate esters, the photoproduced free radicals
halogen compound, resulting in a reduction in or loss of cause free radical polymerization of the ethylenically unsatu
photosensitivity, e.g. premature acid formation. Other known rated monomer. Tacky polymerized areas are made nontacky
sensitizers, such as the cyanine dyes, are salts of strong acids by toner powder development, revealing the image. The un
and weak bases which, because of their acidity, will react with polymerized and unexposed areas may be transferred to plain
acid sensitive components in the photosensitive system during 40 paper and then powder developed to give a copy of the
storage. Moreover, because dyes in salt form are generally in original light image. The unpolymerized monomer may also be
soluble in organic solvents, they are often difficult to formu transferred to a water receptive metal surface and then
late and coat. Many can be made only by complicated synthes polymerized to produce a lithographic plate. In still another
is and are expensive to prepare and to purify. Leuco dye bases, application the photoproduced acid is used to effect the
besides being basic, are sensitive to oxygen and are therefore 45 bleaching of dyes, resulting in high resolution positive or nonr
difficult to purify and to store. The yellow azo compounds are eversal copies of transparent graphic originals.
restricted in their absorption of light and in many cases do not The sensitized systems of this invention are also useful in
effectively sensitize organic halogen compounds. conjunction with tetrahydropyranyl derivatives of aromatic
It is therefore an object of this invention to provide a novel hydroxy and amino compounds, the photoproduced acid caus
sensitized photosensitive element having photolyzable organic 50 ing decomposition of these derivatives to generate the parent
halogen compounds. hydroxy or amino compounds which are capable of reducing
Another object of this invention is to provide sensitized silver or other metal complexes to form visible images.
compositions containing photolyzable organic halogen com Photosensitive films incorporating organic halogen com
pounds. pounds which undergo photodecomposition may also be sen
Still another object of this invention is to provide novel 55 sitized in accordance with this invention. Illustrative
photosensitive copysheets and improved processes for their photosensitive films of this type are shown in U.S. Pat. No.
manufacture and use. 3,081,165, their use being described in xerographic image
In accordance with this invention it has been found that recording processes characterized as "electrochemography'.
photolyzable organic halogen compounds are sensitized to In these processes an electrostatic latent image is formed by
higher wavelengths of light in solution by one or more non 60 exposure of an electrochemographically sensitive surface or
basic propenone compounds. These sensitizers are desirably layer to yield a conductivity latent image adapted to produce
essentially unreactive with said organic halogen compounds in an electrostatic latent image by selective dissipation of an
the dark under ambient conditions, i.e. they are stable for electrostatic surface charge, either once or repetitively
periods of at least 3 months, preferably at least 6 months, without the necessity for successive exposures to an optical
under ambient conditions in the dark. For example, they are 65 image.
most preferably free of alkylamino groups which react with or Although the concentration ratio of sensitizer to organic
ganic halogen compounds in the absence of light. halogen compound is not critical, generally the molar ratio is
The propenone compounds in this invention are ketones of between 1/20 to 2/1, respectively, for maximum speed.
the formula -R1 O Coatings, layers, films or sheets made with solutions of these
N 70 organic halogen compounds and sensitizers, normally with a
binder, are unusually stable and can be stored for long periods
-R?
wherein R and R are either aromatic radicals e.g. phenyl,
under ordinary room conditions. The resulting constructions
absorb light well into the visible light spectrum. These sen
naphthyl, or other aryl radicals) or together form a 5 or 6
membered heterocyclic ring (e.g. carbazole, phenothiazine, 75 sitizers are soluble in organic solvents such as acetone, ethyl
ethyl ketone, monomethyl ether of ethylene glycol, etc. and
phenoxazine), Ar is a divalent aromatic radical (preferably are easily prepared and purified. Moreover, the high efficien
phenylene or biphenylene), n is 1 or 2, and R is an aromatic or cy of these sensitizers makes it possible to use less expensive
 3,617,288
3
and nontoxic organic halogen compounds.
The following examples will illustrate the invention.
To a stirred solution of 37.5 g (0.137 mol) of p-diphen- 217-218 412
ylaminobenzaldehyde, prepared as described by Baker et al. in ala
J. Organic Chem. 30, 3717 (1965), and 23.0 g (0.153 mol) of 5
p-methoxyacetophenone in 200 ml. 95 percent ethanol at 35
C. was added dropwise 15 ml. of a 50 percent aqueous potassi- CHO
um hydroxide solution (0.170 mol). After continuing the stir
ring overnight the bright yellow crystals were filtered off, ma -O CH3 132-134 405
washed with ethanol and air dried. 51.5 g. (92.5 percent yield) 10
of crude product (m.p. 140-145 C.) was obtained. This CH3
product was taken up in hot benzene, treated with charcoal,
filtered and diluted with half its volume of hexane and allowed -CH3 149-50 42
to crystallize. The pure product (39.0 g., 70 percent yield) was
1-(p-methoxyphenyl)-3-(p-diphenylaminophynyl)-2-propen- 15 ÖH,
1-one, m.p. 146-147 C. - - - -- - am - - -
Using the above general procedure the dyes of Table I were The sensitizing dyes in table I were added to the following
prepared. formulation and coatings were prepared on a polyester film
base using a standard knife coating apparatus set at an orifice
20 of 3.0 mils.
TABLE I 5 weight percent cellulose
acetate butyrate in acetone 3.0 grams
N O 1-(2-tetrahydropyranyloxy)-

{ X/
N( )-CH=CH-3r 25
by naphthalene
Sensitizing dye
8:a:
0.005 gram
Samples of the dried coatings were exposed to tungsten light
Melting Maximum through a Corning glass filter that allowed light of wavelengths
R (point
C.) absorption
in ethanol (A.) greater than 390 millimicrons to pass. After exposure, the ex
30 posed samples were placed in face to face contact with a
( > receptor sheet containing a coating of
/ Silver beherate 12.6 parts by weight
-( >-N 10-12 425 Phthalazinone toner
2,6-di-t-butyl-4-methyl phenol
5.2 parts by weight
2.2. parts be weight
Polyvinylbutyra binder I9.8 parts by weight
35 Zinc oxide 50.0 parts by weight
Polyterpene resin 10.0 parts by weight
and then heated at 110° C., for about 10 seconds. The
S
51-52 423 liberated 4-methoxy-11-naphthol caused selectiveo reduction
of the silver behenate in the exposed areas to give a dense
SCH 40 black on white negative copy of the original.
-- 3 148-49 420 Table II lists the exposure intensity required for each coat
ing to obtain a silver image density on the receptor sheet of ap
-(D-o CH 146-147 43 proximately 1.0, indicating the increase in sensitivity over the
control sample with no sensitizing dye.
TABLE II
Exposure in foot
Example Dye candie-seconds
Control.-----. No dye (Control)------------------------------------ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - No image at 540,000.
l--

2- - - - - - - - - - - - -
-v-

( )-N-(D-CH=CHco-(D-N-( ))
/ w V 2
10,000.

15,000.

3-- - - - - - - - - - - -
(C) C-clonel
/
Y
--N -CH=CHCO-
S
- SCH
15,000.
2 w

4- - - - - - - - - - - - - / N 15,000.
( A-N-
/ o >-ch-chco-( >-och,
5- - - - - - - - - - - - - 50,000.

}-N-( )
( >}-N-( -N -CH=CHCO

6- - - - - - - - - - - - - N 40,000.
--s-N- -CH=CHCO- -O CH3
/. - Pro

O CH3
7- - - - - - - - - - - - - CH
Y-N- -CH=CHCO- CH 30,000.
 3,617,288
5 6
EXAMPLE 8 What is claimed is:
1. In a photosensitive composition containing a photolyza
Pentaerythritol tetraacrylate 5.0 grams
ble organic halogen compound having a polarographic half
Cellulose Acetate Butyrate (26% wave reduction potential above about -0.9, at least one sen
butyryl, 20.5% acetyl, 2.5% sitizer comprising a nonbasic propenone of the formula
hydroxyl, melting point 215-220° C.) 1.75 grams
(p-methoxy)-3-(p-diphenylamino
-propen-1-one TT 0.050gram
1,3,5-tris-(tribromomethyl)-s-
triazine 0.37 gram
Acetone 50 m, O

The above solution was prepared and coated 3.0 mils wet on 3 wherein R and R are either aromatic radicals or together
mil polyester in the dark. The dried, tacky coating was pres form a 5- or 6-membered heterocyclic ring, n is one or two, R.
sure laminated with one mil polyester, and exposed imagewise 15 is an aromatic or heterocyclic radical free of electron
to 4000 foot candle seconds oftungsten illumination. The pro withdrawing groups, and Aris a divalent aromatic radical, said
tective film was removed and the photopolymer sheet dusted nonbasic propenone being free of amino groups more basic
with toner powder and fused at 150° C. to give a well defined than the diphenylamino radical and being essentially unreac
positive image of the original, tive with said organic halogen compound in the dark under
20 ambient conditions.
EXAMPLE9 2. The photosensitive composition of claim in which said
photolyzable organic halogen compounds are normally non
gaseous compounds.
N-benzoyl-leucomethylene blue 3. A photosensitive layer containing the photosensitive
(prepared as described in U.S. composition of claim 1.
Pat. No. 2,909,520) t.0 gram 25
Dibromotetrachloroethane 1.0 gram 4. The photosensitive composition of claim 1 in which said
Cellulose Acetate Butyrate (26% composition is capable of a chemical change in the presence
butyryl, 20.5% acetyl, 2.5% of either free radical halogen or acid.
hydroxyl, melting point 215-220 C.) 0.5 gram 5. The photosensitive composition of claim 1 in which said
1-(p-methoxyphenyl)-3-(p-dimethyl
aminophenyl)2-propen-1-one 0.01 gram 30 composition contains a photopolymerizable monomer.
Acetone 0 in. 6. The photosensitive composition of claim 1 in which said
composition contains a compound which is capable of chang
ing color in acid environment.
The above solution was prepared and knife coated 1.0 mil 7. The photosensitive composition of claim 1 in which the
thick on polyester film in the dark. Contact exposure through 35 molar ratio of said sensitizer to said organic halogen com
a negative 6 inches from a photo flood lamp for 10 seconds pound is from 1720 to 2/1.
gave a well defined green negative image of the original, which 8. An image recording element which contains at least one
could be rendered light insensitive by heated at 150° C. for 2 layer comprising the photosensitive composition of claim 1.
minutes to remove the halogen compound.
40

45

50

55

60

65

70

75
 UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,617,288 Dated November 2, 197l
Inventor(s) Richard B. Hartman and George H. Smith
It is certified that error appears in the above-identified patent
and that said Letters Patent are hereby corrected as shown below:

Column 2, line 74, "ethyl" should be --methyl--;

Column l, line 38, "4-methoxy-ll-naphthol" should be
--4-methoxy-i-naphthol--;
Column 5, line 7, "l (p-methoxy)-" should be
--(p-methoxyphenyl)- --.

Signed and sealed this 22nd day of May 1973.

(SEAL)
Attest :

EDWARD M. FLETCHER, JR. . ... ROBERT GOTTSCHALK

Attesting Officer Commissioner of Patents

ForM PO-1050 (10-69) UscoMMs c 6037 6-ro sg

U.S. GoweRNMENT pring office: 969 o-366-334