Organic Photoconductor With Carboxy Group Containing Fluorene Or Fluorore

Abstract

Photosensitive material for electrophotography containing as a sensitizer the compounds of the formula: ##SPC1## Wherein R.sub.1, R.sub.2 and R.sub.3 are selected from the group consisting of nitro, cyano, halogen, trifluoro-methyl, acyl, lower alkyl, lower alkoxy, aryl, aralkyl, and hydrogen; X is selected from the group consisting of oxygen and malononitrile; R.sub.4 is selected from the group consisting of, substituted or non-substituted, alkyloxy, alkylamino, aralkyloxy, aralkylamino, aryloxy, and arylamino; and R.sub.1, R.sub.2, R.sub.3 may be the same or different.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to photosensitive materials for electrophotography. More particularly, it relates to the addition of electron acceptive compounds for sensitizing an organic photoconductive material.

2. Description of the Prior Art

It is known that a number of organic compounds are used in preparing a photoconductive member for electrophotography, While these organic compounds have several advantages as compared with inorganic photoconductive compounds, they have yet some drawbacks to be removed. A serious drawback is that they are of extremely low sensitivity and in most cases their maximum absorption of spectra are without the range of ultraviolet rays and thus they cannot be conveniently employed in practical uses.

It is also known that the above drawback may be avoided by adding to the organic photoconductive member electro acceptive compounds which are called .pi. acid or Lewis acid. For example, as described in Japanese Pat. Publication No. 16587/1967, the addition of less than 10mol% of an electron acceptive compound to an organic photoconductive material provides particularly high photosensitivity for the range of ultraviolet rays. In U.S. Pat. No. 3,484,237, a large amount of electron acceptive compound is added, i.e. 49 to 123 mol% of trinitro fluorenone as the electron acceptive compound is added to poly-9-vinylcarbazole of organic photoconductive material to provide high sensitivity for white light.

However, since the electron acceptor compounds as used in such sensitizing methods have strong polar groups, they are generally insoluble in organic solvents or easily crystallized. Thus, the kinds of solvents which can be used, are disadvantageously limited and it is therefore difficult to select arbitarily in preparing a photosensitive layer a suitable solvent for the preparation conditions thereof. In addition, since the electron acceptor compounds crystallize markedly easily when their solvents vaporize at coating step, it is difficult to form an even photosensitive layer. Furthermore, since the electron acceptor compounds are slightly soluble, the amount of the electron acceptor compound to be added, is limited and it often follows that the sensitizing effect of the electron acceptor compound cannot be completely attained in practical usages. Furthermore, since the comparativity of the electron acceptor compound with the organic photoconductive material is low, the electron acceptor compound crystallizes on the surface of photosensitive layer after a relatively short storage period, and now they cannot be used.

SUMMARY OF THE INVENTION

An object of this invention is to provide novel electron acceptor compounds which can be used as a sensitizer in combination with organic photoconductive materials.

Another object of this invention is to improve the solubility of electron acceptor compounds in organic solvents so as to increase the amount of the electron acceptor compound to be added and the kinds of solvents to be used.

Further object of this invention is to increase the comparativity of electron acceptor compound in photoconductive layer so as to stabilize the photosensitive layer over a long period of time.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The above objects can be achieved by using electron acceptor compounds of the formula: ##SPC2##

wherein R.sub.1, R.sub.2 and R.sub.3 are nitro, cyano, halogen, trifluoromethyl, acyl, lower alkyl, lower alkoxy, aryl, aralkyl, or hydrogen; X is oxygen or malononitrile group connected by double bond; R.sub.4 is substituted or non-substituted, alkyloxy, alkylamino, aralkyloxy; aralkylamino, aryloxy or arylamino group containing 4 to 30 carbon atoms; and R.sub.1, R.sub.2 and R.sub.3 may be the same or different and furthermore the carbon number of the lower alkyl or lower alkoxy group is preferably 1 to 6 from the standpoint of easy production.

The additional advantage which is brought about by using the above compounds, is that there may be reduced or completely removed plasticizers which are added in the preparation of photosensitive layer and which are apt to reduce the sensitivity of the photosensitive layer.

The representatives are used herein may be given below.

1. 7-nitro-9-fluorenone-1-carboxylic acid butyl ester

2. 4-nitro-9-fluorenone-1-carboxylic acid octyl amide

3. 2,7-dinitro-9-fluorenone-1-carboxylic acid-3-methyl-4-isopropylphenyl ester

4. 3-nitro-6-bromo-9-fluorenone-1carboxylic acid P-isopropylbenzyl ester

5. 2-nitro-6,7-dichloro-9-fluorenone-1-carboxylic acid dihexyl amide

6. 2,7-dichloro-9-fluorenone-1-carboxylic acid benzyl amide

7. 2,6,7-tribromo-9-fluoreneone-1-carboxylic acid lauryl amide

8. 7-cyano-9-fluorenone-1-carboxylic acid 4-chlorobutyl ester

9. 7-nitro-9-fluoreneone-2-carboxylic acid cetyl amide

10. 4,5,7-trinitro-9-fluorenone-2-carboxylic acid octyl ester

11. 2,7-dichloro-9-fluorenone-3-carboxylic acid P-anisidino

12. 2-cyano -9-fluorenone-3-carboxylic acid P-aceto-phenyl ester

13. 2,7-dinitro-9-fluroenone-4-carboxylic acid hexyl ester

14. 2,5,7-trinitro-9-fluorenone-4-carboxylic acid lauryl ester

15. 2,7-dichloro-9-fluorenone-4-carboxylic acid 2-P-chlorophenoxyethyl ester

16. 2,7,-dicyano-9-fluorenone-4-carboxylic acid N-methyl-N-dodecyl amide

17. 2-benzoyl-7-nitro-9-fluorenone-4-carboxylic acid 2-ethoxylethyl amide

18. 2-nitro-6-cyano-9-fluorenone-1-carboxylic acid ceryl ester

19. 4,5-dinitro-7-acetyl-9-fluorenone-2-carboxylic acid P-chlorobenzyl ester

20. 4,5,7-trinitro-9-fluorenone-2-carboxylic acid decyl amide

21. 7-chloro-8-methyl-9-fluorenone-2-carboxylic acid hexyl amide

22. 4,5-dichloro-7-methoxy-9-fluorenone-2-carboxylic acid stearly ester

23. 2-benzyl-5,7-dinitro-9-fluorenone-4-carboxylic acid tetradecyl amide

24. 8-trifluoromethyl-9-fluorenone-2-carboxylic acid crotyl ester

24. 2,7-dinitro-9-dicyanomethylene fluorene-4-carboxylic acid hexyl ester

26. 2-cyano-9-dicyanomethylene fluorene-3-carboxylic acid ethoxyethyl ester

27. 1,6-dichloro-9-dicyanomethylene fluorene-4-carboxylic acid myristyl ester

28. 6,7-dibromo-9-dicyanomethylene fluorene-1-carboxylic acid 3,4-xylidide

29. 2,5,7-trinitro-9-dicyanomethylene fluorene-4-carboxylic acid stearyl amide

30. 4,5,7-trinitro-9-dicyanomethylene fluorene-2-carboxylic acid oleyl ester

The above compounds may be generally prepared from the corresponding 9-fluorenone carboxylic acids and 9-fluorenone carboxylic acid ester or amide derivatives may be prepared according to conventional methods of preparing ester or amide. 9-dicyanomethylene fluorenone carboxylic acid ester and amide derivatives may be prepared by reacting the corresponding 9-fluorenone carboxylic acid with malononitrile and thereafter esterifying or forming amido, or by reacting 9-fluorenone carboxylic acid ester or amido derivatives with malononitrile.

The typical methods of preparing the above compounds are given below.

Preparation Example 1

2,7-dinitro-9-fluorenone - 4 -carboxylic acid hexyl ester [(13) of the above mentioned compounds]

3.14g (0.01 mol) of 2,7 - dinitro - 9 - fluorenone -4 - carboxylic acid was dissolved in 50 ml of hexyl alcohol by heating and, after adding three drops of sulfuric acid, was kept at 150.degree.C for 4 hours. After cooling, the precipitated yellow crystal was filtered and the filtrate was distilled to dryness under reduced pressure. The residue was recrystallized with the above crystal from n - hexane and thus there was obtained 2,86g of the end product. Elemental analysis:

Elemental analysis: Calc. Found C 60.29% 60.40% H 4.56% 4.51% N 7.03% 6.98%

Preparation Example 2

2,7 - dinitro - 9 -dicyano - methylene fluorenone -4 - carboxylic acid hexyl ester (25)

3.98g (0.01 mol) of 2,7 - dinitro - 9 -fluorenone -4 - carboxylic acid hexyl ester was refluxed with heating in 200 ml of methyl alcohol and, after adding 1.98g (0.03 mol) of malononitrile and 2 drops of piperidine, was further refluxed for 20 hours. After distilling the solvent, it was recrystallized from n - hexane and there was then obtained 3.03g of the end product. Elemental analysis:

______________________________________ Elemental analysis: Calc. Found ______________________________________ C 61.87% 61.52% H 4.07% 3.99% O 12.55% 12.48% ______________________________________

Preparation Example 3

4,5,7 - trinitro - 9 - fluorenone - 2 - carboxylic acid octyl ester (10)

3.59g (0.01 mol) of 4,5,7 - trinitro - 9 - fluorenone - 2 - carboxylic acid was refluxed in 30ml of thionyl chloride for 5 hours and dried by distilling excess thionyl chloride. The acid chloride so obtained was heated in 50 ml of octyl alcohol at 80.degree.C for 3 hours and then octyl alcohol was distilled under reduced pressure. The residue was recrystallized from hexane and there was thus 3.63g of light yellow end product. Elemental analysis:

______________________________________ Elemental analysis: Calc. Found ______________________________________ C 56.04% 56.17% H 4.50% 4.46% O 8.91% 8.86% ______________________________________

Preparation Example 4

4,5,7 - trinitro - 9 - fluorenone - 2 - carboxylic decyl amide (20)

3.78g (0.01 mol) 0f 4,5,7-trinitro-9-flurorenone-2-carboxylic acid chloride as prepared in preparation Example 3 was heated with 50 ml of decylamine at 80.degree.C for 3 hours and decylamine was distilled under reduced pressure. The residue was recrystallized from hexane and there was obtained 4.06g of a light yellow end product. Elemental analysis:

______________________________________ Elemental analysis: Calc. Found ______________________________________ C 57.82% 57.71% H 5.27% 5.32% O 11.24% 11.20% ______________________________________

Preparation Example 5

1,6-dichloro-9-dicyano-methylene fluorenone-4-carboxylic myristil ester (27)

2.93g (0.01 mol) of 1,6-dichloro-9-fluorenone-4-carboxylic acid was refluxed in 300 ml of methyl alchohol and after adding 2.0g (0.03 mol) of malononitrile and 2 drops of piperidine, was refluxed for additional 20 hours. After cooling, the precipitated crystal was filtered and there was then obtained 2.31g of 1,6-dichloro-9-dicyanomethylene fluorenone 4-carboxylic acid it refluxed in 30 ml of thionyl chloride for 5 hours to form the corresponding acid chloride.

After distilling excess thionyl chloride, it was refluxed in 40 ml of myristyl alcohol at 80.degree.C for 3 hours and after distilling myristyl alcohol under reduced pressure, it was recrystallized from N-hexane and there was then obtained 3.18g of the end product. Elemental analysis:

______________________________________ Elemental analysis: Calc. Found ______________________________________ C 69.26% 69.31% H 6.39% 6.35% N 5.21% 5.30% Cl 13.19% 13.12% ______________________________________

Organic photoconductive materials as herein used are preferably such as to act as the electron donative member as the above compounds when combined with organic photoconductive materials can act as the electron acceptor member. Thus they include low molucular type organic photoconductive materials such as amyl hydrazone derivatives, oxadiazole derivatives, pyrazoline derivatives, imidazolone derivatives, imidazolinethione derivatives, benzimidazole derivatives, benzoxazole derivatives, and benthiazole derivatives; polymer containing heterocylic ring such as carbazole ring or polynulclear aromatic rings such as naphthalene ring or anthrathene ring which are disclosed for example in Japanese Pat. Publication Nos. 10966/1959, 812/1961, 18674/1967, 25230/1967 and the like.

Representative materials used as an organic photoconductive material in the present invention are as follows:

A. polymer having a carbazole ring such as poly-9-vinylcarbazole, 9-vinylcarbazole copolymer, 3-nitro-9-vinylcarbazole copolymer, 3-methylamino-9-vinylcarbazole copolymer, nitrated poly-9-vinylcarbazole, 3,6-dibromo-9-vinylcarbazole copolymer, poly-9-vinyl-3-aminocarbazole, chlorinated poly-9-vinylcarbazole, thiocyanated poly-9-vinylcarbazole, cyanated poly-9-vinylcarbazole, brominated poly-9-vinylcarbazole, 3-iodo-9-vinylcarbazole copolymer, poly-3,6-diiodo-9-vinylcarbazole, poly-3-benzylideneamino-9-vinylcarbazole, 3,6-dibromo-9-vinylcarbazole copolymer, .alpha..omega.-bis-carbazole-alkane derivative, vinyl anthracene . 9-vinylcarbazole copolymer, (2 or 3)-vinyl-9-alkyl-carbazole polymer or copolymer (the alkyl group is selected from the group consisting of primary alkyls such as methyl, ethyl and propyl).

B. aromatic amino derivatives such as amino-polyphenyl, (allylidene) azines, N-N'-dialkyl-N, N'-dibenzylphenylenediamine, N,N,N',N'-tetrabenzyl-phenylenediamine, N,N'-diphenyl-P-Phenylenediamine, N,N'-dinaphtyl-p-phenylenediamine, 4,4-dimethylaminophendiphenone.

C. diphenylmethanes and triphenylmethanes such as diphenylmethane dye dye leuco base and triphenylmethane dye leuco base.

D. heterocyclic compounds such as oxadiazole, 5-aminothiazole, 4,1,2-triazole, imidazolone, oxazole, imidazole, pyrazoline, imidazoline, polyphenylenethiazole, 1,6-methoxyphenezine, pyrazolinopyrazoline derivatives and the like.

E. compounds having a condensed ring such as benzothiazole, benzimidazole, and benzoxazole, for example, -tetraphenylhexatriene, 2-(4'-diaminophenyl-benzoxazole and 2-(4'-dimethylaminophenyl) benzoxazole, aminoacridine, quinoxaline, diphenylenehydrazones, pyrrocoline derivatives, 9,10-dihydroanthracene derivatives and the like.

F. compounds having a double bond such as acylhydrazone, ethylene derivatives, 1,1,6,6-tetraphenylhextraiene, and the like.

G. condensation products such as condensation products of aldehydes and aromatic amines, reaction product of secondary aromatic amines and aromatic halides, polypyromethane-imidopoly-p-phenylene-1,3,4-oxadiazole and the like.

H. vinyl polymers (except polyvinylcarbazole) such as .alpha.-alkylacrylic acid, amide polymers polyvinylacridine, poly-[1,5-diphenyl-3-(4-vinylphenyl)-2-pyrazoline], poly-(1,5-diphenylpyrazoline), polyacenaphthylene, neuclear substituted polyacenaphthylene, polyvinylanthracene, poly-2-vinyldibenzothiophene and the like.

Materials providing good results of sensitizing treatment of this invention among these organic photoconductive materials are polymers having a carbazole ring and their derivatives, aromatic amino derivatives, diphenylmethane derivatives and triphenylmethane derivatives.

In practising this invention, the organic photoconductive materials and the compounds of this invention are dissolved in proper solvents. The compounds of this invention may be dissolved in numerous kinds of solvents and thus the most proper solvent may be selected from numerous solvents depending upon an organic photoconductive material to be used. The amount of the compound of this invention varies depending upon the purpose thereof. For example, where it is coated on a substrate such as paper, film, and the like and used as an almost colorless or almost colorless, transparent photosensitive layer, it is added within the ratio of 0.01 to 10 mol, preferably 0.1 to 5 mol per 100 mol of organic photoconductive material (if the photoconductive material is a polymer, it is calculated based upon the molecular weight of unit monomer of the polymer). In this case, high photosensitivity for ultraviolet range is provided. If high sensitivity for visible light is also required, it may be achieved by adding dye sensitizers in such an amount not to color strongly the photosensitive layer.

If high sensitivity for white light color is needed as in a master photosensitive plate and if coloration of the photosensitive plate is negligible, high ratio of 10 to 120 mol per 100 mol of organic photoconductive material may be used to provide high sensitivity for visible light. The solution containing the photoconductive material and the compounds of this invention may if necessary include binder resins and other additives, which are coated on a substrate or some special cases used in the form of self-substrate.

The following examples illustrate the embodiments of this invention, but do not limit the scope of the invention. Comparison Example 1

To the solutions prepared by dissolving 2.0g of poly9-vinylcarbazole in 30ml of the following solvents were added 2,4,7-trinitro fluorenone (TNF) of 10 mol% and 100 mol% based of poly-9-vinylcarbazole. The solubility of TNF in the solvents were measured and indicated in Table below, wherein reference symbol O means that TNF is soluble and X means that TNF is insoluble.

______________________________________ TNF 100 mol % of the compounds as Solvent 10 mol % 100 mol % listed above ______________________________________ Chlorobenzene X X O Tetrahydrofuran O X O Cyclohexane O X O Pyridine O O O Dimethylform- O O O amide (DMF) Dioxane O X O 1,2-dichloro- O X O ethane Methylene- O X O Chloride Chloroform X X O Toluene X X O Benzene X X O Carbon disulfide X X O ______________________________________

Comparison Example 2

The solutions prepared by dissolving 2g of polyvinyl carbazole and 1.63g of 2,4,7-trinitrofuruorenone in 30ml of dimethylformamide were coated on an Al plate and dried at 120.degree.C for 10 minutes to form a 13.mu. thick photosensitive layer. Upon allowing the photossnsitive layer to stand in a dark place for one week, it was observed that 2,4,7-trinitrofluoroenone was crystallized and precipitated. Moreover, in this example, where a photosensitive layer was formed using a solution containing 3.26g of 2,4,7-trinitrofluorenone, it was observed that 2,4,7- trinitrofluorenone was crystallized and predipitated immediately after the formation of photosensitive layer. Precipitation due to crystallization is judged from opaqueness of the photosensitive layer and unevenness of the surface thereof. In this comparison example, where the above compounds (1) to (30) were used in place of 2,4,7-trinitrofluorenone, no precipitation due to crystallization was observed. In addition, pyridine was used in place of dimethyl-formamide with similar results. Comparison Example 3

Three photosensitive layers comprising polyvinylcarbazole; polyvinylcarbazole, and 2,4,7-trinitrofluorenone, and polyvinylcarbazole, 4,5,7-trinitro-9-fluorenone-2-carboxylic acid octyl ester, respectively, were prepared on 75.mu. thick polyester film whose surface was made hydrophilic, by coating. The thickness of the resulting photosensitive layer was adjusted to 4.mu. thickness. By winding the polyester film around the rods having the following diameters with the surface thereof outward, cracking of the photosensitive layer was tested. In Table below, reference symbol X means that the cracking of photosensitive layer occurs and O means that no cracking occurs.

__________________________________________________________________________ Diameter PVK TNF 4,5,7-trinitro- (mm) (not added) 9-fluorenone-2- carboxylic acid octyl ester 10 mol% 100 mol% 10 mol% 100 mol% __________________________________________________________________________ 6 O O O O O 5 0 O X O O 4 X X X O O 3 X X X X O __________________________________________________________________________

EXAMPLE 1

A solution composed of 2g of 1,3,5-triphenylpyrazoline, 2g of polyvinyl butyral resin, 70.4mg. of 7-cyano-9-fluroenone-1-carboxylic acid 4-chlorobutyl ester [compound (8)] and 50 ml of ethanol was coated on an aluminum laminated paper to form a layer of about 6.mu. thickness, when dried, and dried to form a photosensitive paper. Then the photosensitive paper so formed was charged in dark place and exposed to light through a positive microfilm original pattern with a film enlarging unit equipped with 500W tungusten lamp. It was developed with a liquid developer and there was then obtained excellent positive image. Proper exposure amount was 600 Lux sec. Example 2

A solution composed of 2g of N,N,N',N'-tetrabenzyl-m-phenylenediamine, 2g of polystyrene, 144mg of 2,5,7-trinitro-9-dicyanomethylene fluorenone-4-carboxylic acid stearyl amide (compound (29) ) and 40ml of toluene was coated on a paper which was treated not to permeate solvent, and dried to provide a photosensitive paper. The thickness of the photosensitive layer was about 7.mu..

The photosensitive layer was charged, exposed to light, and developed as in Example 1 and there was thus obtained an excellent image. The proper exposure amount was 550 Lux sec.

EXAMPLE 3

A solution prepared by dissolving 2g of poly-3-methyl-9-vinylcarbazole and 38mg of 2,7,-dinitro-9-fluoroenone-4-carboxylic acid hexyl ester [ compound (13) ] in 35ml of chlorobenzene and a solution prepared by dissolving 11.6mg. of 9,9'-diethyl-3,3'-dicarbazolyl-phenylmethyliodide (sensitizing dye) in 5ml of methylene chloride were mixed to prepare a photosensitive solution. The photosensitive solution was coated on a transparent polyester film on which aluminum was thinly deposited, and dried to form a transparent photosensitive film having a 6.mu. thick photosensitive layer. The photosensitive layer so prepared was charged, exposed to light and developed as in Example 1 and there was then obtained an excellent copied image. The proper exposure amount was 150 Lux sec.

EXAMPLE 4

A solution composed of 2g of poly-9-vinylcarbazole, 4.9g of 4,5,7-trinitro-9-fluorenone-2-carboxylic acid octyl ester [ compound (10) ] and 30ml of chlorobenzene was coated on an aluminum plate to form a 10.mu. thick dry layer. The photosensitive plate so prepared was applied to a rotation type electrometer and after charging negatively at -6KV, exposed to a tungusten lamp (effective illumination intensity, 14.4 Lux ). Exposure amount required for decaying the initial potential 950V to 1/2 thereof (half-decay exposure) was 4.4 Lux sec.

In this example, where polyl-3-chloro-9-vinyl-carbazole was used in place of poly-9-vinylcarbazole, half-decay exposure was 4.0 Lux sec. and where poly-3,6-chloro-9 -vinylcarbazole was used, the half-decay exposure was 3.6 Lux sec.

EXAMPLES 5 to 10

The following compounds were used in place of 4,5,7-trinitro-9-fluorenone-2-carboxylic acid octyl ester in Example 4 to prepare photosensitive plates. Half-decay exposure of the photosensitive plates were measured as in Example 4 with Electrometer with the results as shown below. Example added Amount (mol% based Initial Half-decay compound on poly-9-vinyl potential exposure carbazole) __________________________________________________________________________ 5 compound 1 4.04g (120 mol%) 92OV 5.2 Lux sec. 6 do. 5 5.40g (100 do.) 950V 5.0 do. 7 do. 15 3.71g (80 do.) 880V 6.0 do. 8 do. 17 2.39g (50 do.) 900V 11.0 do. 9 do. 25 1.39g (30 do.) 960V 18.5 do. 10 do. 30 1.36g (20 do.) 960V 24.0 do. __________________________________________________________________________

Claims

We claim:

1. Photosensitive material for electrophotography comprising one or more organic photoconductive materials and one or more compounds of the formula: ##SPC3##

wherein R.sub.1, R.sub.2, and R.sub.3 are, the same or different, nitro, cyano, halogen, trifluoromethyl, acyl, lower alkyl, lower alkoxy, aryl, aralkyl, or hydrogen; X is oxygen or malononitrile; and R.sub.4 is, substituted or non-substituted, alkyloxy, alkylamino, aralkyloxy, aralkylamino, aryloxy, or arylamino, containing 4 to 30 carbon atoms, the ratio of said compound to said organic photoconductive material being 0.01 - 120 mols to 100 mols.

2. Photosensitive material for electrophotography according to claim 1 in which the compound represented by the formula of claim 1 is added in a ratio of 0.01 to 10 mol per 100 mol of the organic photoconductive material.

3. Photosensitive plate for electrophotography comprising one or more organic photoconductive materials and one or more compounds of for sensitizing said photoconductive materials of the formula: ##SPC4##

wherein R.sub.1, R.sub.2, and R.sub.3 are, the same or different, nitro, cyano, halogen, trifluoromethyl, acyl, lower alkyl, lower alkoxy, aryl, aralkyl, or hydrogen; X is oxygen or malononitrile; and R.sub.4 is, substituted or non-substituted, alkyloxy, alkylamino, aralkykoxy, aralkylamino, aryloxy, or arylamino, containing 4 to 30 carbon atoms, the ratio of the compound to the organic photoconductive material being 10 to 120 mols to 100 mols.