Powerpoint Organic Pigments

PIGMENT

Pigment •

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What is pigment A pigment is a material that changes the color of reflected or transmitted light as the result of wavelength-selective absorption. This physical process differs from fluorescence, phosphorescence, and other forms of luminescence, in which a material emits light Many materials selectively absorb certain wavelengths of  light. Materials that humans have chosen and developed for use as pigments usually have special properties that make them ideal for coloring other materials. A pigment must have a high tinting strength relative to the materials it colors. It must be stable in solid form at ambient temperatures.

Pigment •

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What is pigment A pigment is a material that changes the color of reflected or transmitted light as the result of wavelength-selective absorption. This physical process differs from fluorescence, phosphorescence, and other forms of luminescence, in which a material emits light Many materials selectively absorb certain wavelengths of  light. Materials that humans have chosen and developed for use as pigments usually have special properties that make them ideal for coloring other materials. A pigment must have a high tinting strength relative to the materials it colors. It must be stable in solid form at ambient temperatures.

PIGMENT is a particulate solid dispersed into a medium without solution or significant interaction

Differences between Pigments and Dyes Pigments are dispersions dispersions in medium but dyes are solutions Pigments posses particulate properties properties but dyes do not Pigments are far more durable durable and resistant resistant to fading than dye

Pigment

Dye

Applications of Pigments 1 Inks : water and solvent based 2 Paints : water and solvent based 3 Plastics : all types including EVA 4 Rubber 5 Glass 6 Ceramic 7 Textile 8 Cement Products 9 Cosmetics

Required Properties of Pigments

Colour

Weather Stability

Colour Strength

Opacity

Heat Resistant: IK

Insolubility

Light Fastness: sun light, xenon

Solvent Fastnesss

Color Strength

Full-Tinting Strength

Two Roll Mill

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TEST METHOD

TUJUAN : Untuk memastikan bahwa analisa warna plastik resin PVC dengan two roll mill dilakukan dengan benar

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2. RUANG LINGKUP : Instruksi kerja ini menjelaskan cara kerja analisa warna plastik resin PVC dengan two roll mill yang berlaku untuk produk B-201 pengiriman Maspion atau customer lain yang requirment sejenis.

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3. BAHAN – BAHAN YANG DIPAKAI PVC Soft Natural (Type : EH 1000) TiO2 (Type : Tronox CR-834) DOP (Dioctyl Phthalate) Stabilizer (Methylene Mercaptide) Sample 5. CARA KERJA Pembuatan Compound Timbang bahan untuk bahan untuk campuran compound I dengan komposisi : -. PVC soft = 50gram -. DOP = 5gram -. Stabilizer = 5 gram Kemudian timbang juga bahan untuk bahan untuk campuran compound II dengan komposisi: -. PVC soft = 45 gram -. DOP = 4,5 gram -. Stabilizer= 4,5 gram Buka kran steam ke alat two roll mill yang sudah di set dengan tekanan 2 kg/cm2 untuk mencapai suhu 130C. Set jarak antara two roll mill 0,1 mm dengan fuller dan sesuai tanda batas pada alat. Masukkan bahan compound diatas ke alat two roll mill sambil dilakukan pengadukan. Setelah campuran masuk semua, grinding dan diaduk dengan kape selama 10 menit dengan menjaga besar ukuran compound 5,5 – 6 cm dari pinggir roll. Compound diangkat dan didinginkan pada suhu ruangan.

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Dibuat oleh :

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Pewarnaan Compound I. Timbang sample = 0,0240 gr . Tekanan steam dinaikkan menjadi 2,8  – 3,0 kg/cm2 sampai suhu two roll mill menjadi 140 C Setelah suhu two roll mill mencapai 140 C, masukkan compound campuran I lakukan pengadukan sampai homogen. Masukkan campuran sampel / pigment pelan-pelan ke dalam compound campuran I. Setelah sampel masuk semua lakukan penggilingan dengan two roll mill sambil diaduk-aduk selama 5 menit . Kemudian compound hasil pewarnaan diatas, diangkat dan didinginkan pada suhu ruang.

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Pewarnaan Compound II. 1. Setelah dingin compound hasil pewarnaan I dipotong dan ditimbang = 6,0000 gr ( untuk pewarnaan ke II) Masukkan compound campuran II lakukan pengadukan sampai homogen. Kemudian masukkan compound pewarnaan I yang sudah ditimbang, lakukan penggilingan sambil diadukaduk selama 5 menit. Kemudian compound diangkat dan didinginkan pada suhu ruang. Setelah dingin potong dengan ukuran  3 x 3 cm sebanyak 10 lembar untuk 1 kali press.

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Pressing Setting alat hot press pada suhu 190 C dan diamkan sampai suhu stabil. Mould dibersihkan dan dikeringkan. Taruh potongan compound hasil pewarnaan pada mould dengan standard / pembanding pada posisi keri dan sampel / yang dibandingkan pada posisi kanan. Mould ditutup dan masukkan kedalam hot press. Lakukan pressing dengan tekanan 2,5 Mph suhu 190 C selama 3 menit. Selesai pressing keluarkan mould dari hot press kemudian dinginkan dengan cooling press selama  1 menit. Setelah dingin plate dibuka, lihat hasilnya dan ukur warnanya dengan chromameter.

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Formulir Instruksi Kerja :

Two Roll Mill

Solvent Fastness

Effect of particle size of the pigment 1 Tinting strength 2 Gloss 3 Viscosity 4 Weatherfastness

Forms of Pigments

Solid

Minimum 95% Pigment content

Presscake

Maximum 40 % Pigment Content

Chip, masterbatch

Usually 20-25 % Pigment Content

BASIC / PRIMARY COLOURS (2nd & 3ry ?)

Inorganic Pigments vs Organic Pigments Particular

Inorganic Pigment

Organic pigment

Color

Dull

Bright

Color strength

Low

High

Opacity

Opaque

Transparent

Light Fastness

Good

Vary from poor to good

Heat Fastness

Good

Vary from poor to good

Chemical Fastness Poor

Very Good

Solubility

Insoluble in sovents Have little degree of  solubility

Degree of safety

May be unsafe

Usually safe

Classification of Organic Pigments •

Azo Pigments

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Non-Azo Pigments = Polycyclic Pigments Azo Pigments Azo Pigments have the azo group (-N = N-) There are 2 stages for the synthesis of azo pigments: - Diazonium salt formation - Coupling reaction

Monoazo Yellow and Orange Pigments 1. They are obtained by coupling a diazonium salt with acetoacetic arylides to give greenish to medium Yellow Pigments 2. While coupling with 1 – arylpyrazolones-5 produces reddish orange shade 3. They possess good light fastness but poor solvent & migration resistance 4. Commercial application in certain inks ( flexo & offset inks)

SYNTHESIS of Monoazo yellow

REACTOR

REACTOR

ROTARY VACUUM EVAPORATOR

FILTER PRESS

SYNTHESIS of Monoazo Orange

Disazo Pigments •

Disazo Pigments : 2 classes 1. The coupling coupling of di – and tetra – substituted diaminodiphenyls with acetoacetic arylides or pyrazolones pyrazolones 2. The coupling of diazotization diazotization of aromatic aromatic amines with bisacetoaceticarylides 3. These pigments cover the colour range from greeny yellow to reddish yellow & orange & red 4. They have better solvent & migration fastness than mono azo pigments & are use in printing printing inks inks & plastic plastic

The color potential of disazo pigments covers the color range from very greenish yellow and orange and red

SYNTHESIS of Disazo Pigments(2 Oxygens missing)

β- Naphthol Pigments Beta Naphthol Pigments provide colours from orange to medium red Production by coupling reaction with beta naphthol Solvent resistant, migration fastness & light fastness are comparable to mono azo yellow pigments Commercial application in paints

SYNTHESIS of Beta Naphthol Pigment

Naphthol AS Pigments (Naphthol Reds)

These pigments provide colour from yellowish & medium red to brown & violet They are obtain by coupling reaction of aryl diazonium salt with aryllides of 2-hydroxy-3-naphthoic acid Their solvent fastness & migration resistance marginal Commercial application in printing inks & paints

SYNTHESISof Naphthol AS Pigment (2 N missing)

Azo Pigment Lake (Salt Type Pigments) These pigments provide colours between medium red to bluish red They are from by precipitating a monoazo compound with contain sulfo & / or carboxy groups with metal cations such as calcium, barium, magnesium, strontium or manganese. These pigments have limited light fastness & migration resistance but good heat fastness.

Their commercial application are in printing inks, plastic & paints

SYNTHESIS of Naphthol AS Pigment Lakes

SYNTHESIS of Beta Naphthol Pigment Lakes

SYNTHESIS of Azo Metal Complexes

SYNTHESIS of Bona Pigment Lakes

SYNTHESIS of Naphthalenesulfonate Pigment Lakes

SYNTHESIS of Azomethine Metal Complexes

Benzimidazolone Pigments

These pigments cover the spectrum from greenish yellow to orange & medium red to maroon There two type : the first one is obtain by coupling with 5acetoacetylaminobenzymidazolone,the second one the coupling components is 5-2-hydroxy-3-naphthoaylaminobenzymidazolone Pigment performance including light fastness & weather ability is excellent Application in plastics & hybrid printing inks

SYNTHESIS of Benzimidazolone Pigment (missing 1N) Yellow, Orange

SYNTHESIS of Benzimidazolone Pigment (Red, Brown)

SYNTHESIS of Disazo Condensation Pigments The spectral range of these pigments covers from greenish yellow to orange & blueish red or brown They are obtained from the condensation of two carboxylic monoazo with one aromatic diamine

They have wood solvent & migration resistance & light fastness Application in plastic & spin dyeing

SYNTHESIS of Disazo Condensation Pigments Yellow (missing R, CONHAr)

SYNTHESIS of Disazo Condensation Pigments, Red (missing OH, R)

Isoindolinone & Isoindoline Pigments These pigments produce greenish to reddish yellow They show good light & weather fastness, solvent & migration resistance Commercial application in plastic & high grade coatings

SYNTHESIS of Isoindolinone

SYNTHESIS of Isoindoline Pigments

Polycylic Pigments These are pigments with condendsed aromatic or heterocyclic ring systems They have good light, heat and weather fastness and good solvent and migration resistance They are more expensive than azo pigments except the phthalocyanine pigments They are use in all application ranging from water & solvent base inks, water & solvent base paints, plastic, rubber, cement & textile

Phthalocyanine Pigments

These pigments are the most produced organic pigment in the world. They cover the colour from greenish blue to reddish blue & blueish green to yellowish green They are produce by reacting metal salt with nitrogen source compound & phthalic acid derivative They show good solvent & migration resistance, good , light, heat, chemical & weather fastness Commercial application cover a whole range of product

SYNTHESIS of Phthalocyanine Pigment

Quinacridone Pigments

These pigments available in a reddish violet and a blueish red Like the phthalocyanine pigments ,quinacridone are make in two stages , the preparation of crude quinacridone and the pigmentation the crude They have outstanding light & weather fastness & solvent & migration resistance Commercial application are for high grade coating ( automotive), for plastics & special inks

SYNTHESIS of Quinacridone Pigments

Perylene and Perinone Pigments

The color of perylene is red while for perinone is orange

They provide excellent light , heat and weather fastness

Commercial application are for spin dyeing, polyolefin, special printing inks for metal decoration and poster printing and automotive paints

SYNTHESIS of Perylene Pigments

SYNTHESIS of Perinone

Perinone

Diketopyrrolo Pyrrole (DPP) Pigments They provide colour range from orange to blueish red The pigment consist of two anelated five membered rings each of which contain a carbonamide in the ring They have excellent light and weather fastness as well as good heat stability Commercial application are for plastics and automotive finishes

SYNTHESIS of Diketopyrrolo Pyrrole pigment

Thioindigo Pigments

This is reddish violet shade pigments

They show good light fastness and weather fastness They are generally used in plastics and industrial coating such as automotive finishes

SYNTHESIS of Thioindigo Pigments

Anthrapyrimidine Pigments

This class of pigment provide a greenish to medium yellow coloration

They have excellent heat & weather fastness Commercial application are for industrial coating such as automotive metallic finishes

SYNTHESIS of Anthrapyrimidine

Flavanthrone yellow .the only commercially use flavanthrone is a brilliant reddish yellow

Excellent light and weather fastness combined with good solvent and migration resistance Commercial application for automotive finishes

SYNTHESIS of Flavanthrone

Pyranthrone Pigments

Most pigments are orange but others are blueish red colour These are derivatives of pyranthrone molecule with varying level of halogenation They have good weather fastness Commercial application for high grade industrial finishes.

SYNTHESIS SYNTHESIS of Pyranthrone Pigments

Anthanthrone Pigments

The only commercial pigments is dibromoanthanthrone dibromoanthanthrone which provides shade of scarlet for metallic finishes

They have outstanding weather fastness Commercial application are in high grade

SYNTHESIS SYNTHESIS of Anthanthrone Anthanthrone

Dioxazine Pigments These pigments produced violet colouration and in combination with phthalocyanine blue pigment produces a very reddish shade Dioaxazine Pigments are derived from triphenodioxazine, linear system of five anelated rings They show extreemly light and weather fastness as well as excellent solvent and migration resistance Commercial application include the pigmentation of  plastics, printing inks, spin dyeing and coating

SYNTHESIS of Dioxazine Pigments, violet 23 & 37

Triarylcarbonium Pigments The colour covers from green,violet and victoria blue There are two types of these pigments: salt of triphenylmethane sulfonic acid salt of heteropolyacid with tungsten, molybdenum, silicon or iron They have poor solvent resistance and limited light fastness but have excellent colour brilliant and clarity of hue better than any other organic and /organic pigments Commercial application is for printing inks especially are for packaging inks

SYNTHESIS of Triarylcarbonium Pigments

Quinophthalone Pigments

They are mostly greenish yellow These pigments have a polycylic structure derived from quinaldine and phthalic anhydride They have excellent temperatures resistance The main market for these pigments are in the plastics and coating industries

SYNTHESIS of Quinophthalone

Synthesis of Pigments

Production of CI Pigment Yellow 1, 11680 Diazotization In a vessel 912 kg of 4-methyl-2-nitroaniline is stirred over night with water. Then 3395 L of 5 mol / L HCl is added, together with some ice to lower the temperatures to 0 C. Sodium nitrite solution, 792 L of 40 wt % is then run in underneath the surface. Any excess sodium nitrite is removed by addition of 3- nitro- ptoluidine. Active charcoal is added as clarifying agent and then filtered Dissolution the coupling component AcetoAcetanilide, 1098kg, is strirred with water for 1 H at 25C then 510 kg of CaCO 3 and 206 kg of 33% NaOH solution is then added.

Production of CI Pigment Yellow 1, 11680

Coupling The reaction mixture is heated to 33 C and the clarified diazonium salt solution is then run in. After 30 minutes HCl is added to adjust the pH to 3-4. After 20 minutes the pigment is separated by filtering through a filter press and wash with water to remove salt. The filter cake ( press cake ) is dried at 60-65C The yield is 2042 kg

Production of CI Pigment Red 112, 12370 Diazotization In a steel-enamel stirred tank, 500 kg of glacial acetic acid is heated to 65 C , and 276 kg of 2,4,5-trichloroaniline is added. The soln is run into a mixture of 3500 L of water and 1120 L of 5 mol/L of HCl. The reaction mixture is cooled to 0C by addition of ice and repeatedly diazotizide with 185 L of 40 wt %NaN02 soln. The temp must not exceed 0 C. After 2 h, 107 kg of CaCO3 suspended in water is added, The volume is made up to 28500L with water; active charcoal are added and the soln is filtered thro a clarifying filter.

Dissolution of the coupling component At 30 C, 420 kg of naphthol AS/D is dissolved in 322 L of 33% of  NaOH and 3000L of water ; 10 kg of active charcoal is then added and the soln is filtered. The volume is made up to 14000 L and temp is 20 C. Then 84 g of Igepon T in 200 L of water is added and the mixture is cooled to 3 C with ice. The coupling component is precipitated by rapid addition of  235 L of glacial acetic acid. Coupling The reaction mixture is heated to 38 C, and the filter diazonium salt soln is run in under the surface of the suspension of the coupling component within 3,5 h. After completion of coupling, the pigment is isolated by filtering the suspension thro a press,

Copper Phthalocyanine Blue 

BLUE PIGMENT CuPc (Copper Phthalocyanine) Blue pigment CuPc is one of the most stable pigments towards light, temperature and chemicals and hence, combined with its attractive colors, this pigment is widely used in many applications such as in paints water & solvent based paints including automotive paints), in water & solvent based inks, in textiles and in plastics with temperature of  operations up to 350 C.

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In industry, this pigment is produced in two stages The first stage is the preparation of the Blue Crude CuPc while the 2nd is the Pigmentation of  crude CuPc ie the reduction of particle size of  Crude CuPc.

Copper Phthalocyanine Blue CRUDE CuPc Blue Crude CuPc is commonly prepared by reacting copper chloride urea, phthalic anhydride, catalyst with solvent. •

CuCl + 12 H2NCONH2 + 4 C6H4 (CO)2O

CuPc + NH3 + CO2 + H2O + NH4Cl

(produced in Malaysia)

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Structure of CuPc

Yield 90%

Production of Crude CuPc according to Patent GB476243 Phthalic anhydride 100 kg, urea 135 kg, and trichlorobenzene 300 kg are mixed in 1000 L of vessel equipped with an oil bath and stirrer: 24 kg of  copper(II) chloride and 0.5 kg of ammonium molybdate are then added. The mixture are heated up slowly within 1 hour to 200 C . Gas evolution mostly CO2 and some NH3 with formation of phthalimide begins at 130 C. Formation of CuPc begins at 160-170 C, with simultaneous released of CO and NH3. After stirring at 200-205 C for 1 hour, formation of the pigment is complete. The Phthalocyanine is filtered of ; washed with hot trichlorobenzene at 50 C, methanol and hot water; and dried. The yield of CuPc is 87 kg

GLASS LINED PRESSURE REACTOR

ROTARY VACUUM DRYER

Filter Press

Spin Flash Dryer 

Purchasing

To buy raw materials, machinery, lab equipments, spare parts of machinery and packaging etc

QC

To set the standard and control the quality of the raw materials, finish products and packaging

R&D

To produce new cheap products which satisfy customers requirements based on preliminary research by Technical Support

Production

To produce consistent products

Marketing

To find the market for the products and to set the quarterly sale forecast

Engineering

To repair the damage and worn out parts of machinery

Technical Support

To research customer complains regarding with quality & packaging problems and to prepare test methods for the finish products suitable for customers and to do preliminary research for new products based on customer’s requirements

Product Specification of Crude CuPc Parameter

Specification

Test Method Number

Purity

97 % min

TM 1

Moisture Content

1 % max

TM 2

Water Soluble Matter

1.5 % max

TM 3

Alcohol Soluble Matter

2.0 % max

TM 4

pH

4-8

TM 5

Conductivity

800 mho

TM 6

Total Grit

300 ppm max

TM 7

Iron

20 pieces max /100 g

TM 8

Sand

30 pieces max / 100 g

TM 9

Fiber

Trace

TM 10

Free Copper Content

3000 ppm max

TM 11

PCB

0.1 ppm max

TM 12

PROBLEMS OF MANUFACTURING CRUDE CuPc

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Yield The yield of reaction is max 90% based on copper chloride used (see List of Patents). There are therefore about 10 % of the reagents used are disposed as waste.

Environmental Effect Most of the waste of the production of crude CuPc (11,000 tons/yr) is precipitated using Na 2S and then is buried underground

Pigmentation Process Methods

Pigments Produced

Notes

Dissolving in conc H2SO4 Blue Pigment 15:0 and then sprayed into aqueous solution containing certain additives Blue Pigment 15:1

Reddish blue pigment with heat stability up to 170 C and poor solvent resistant

Blue Pigment 15:2

Reddish blue pigment with heat stability up to 350 C and good solvent resistant

Blue Pigment 15:3

Greenish blue pigment with tendency to agglomerate

Grinding with inorganic salts with the aids of polyol solvent in the presence of  certain additive in kneader or ball mill

Reddish blue pigment with heat stability up to 350 C but poor solvent resistant

Blue Pigment 15-4 Greenish blue pigment with solvent fastness

Kneader for Beta-CuPc

Ball mill for Beta-CuPc

Ball Mill

Pigmentation by Sulfuric Acid Production of alpha  –CuPc Pigment from crude CuPc Crude CuPc 700 kg is added quickly to conc. H2SO4 (96%) 6300 kg , and the temp is allowed to rise to 50 C . The suspension is stirred overnight. When the phthalocyanine is completely dissolved , the suspension is sprayed into 35000 L of water at 70 C, and the temp is allowed to rise to 85 C  – 90 C. The precipitated pigment is filtered off in a filter press and washed until acid free. The presscake is then mixed with 25000 L of water, and the remaining acid is neutralized with K2CO3 and ammonia. After addtion of 35 kg of Lorol sulfonate the suspension is heated for 1 h until a clear filtrate is obtained. After filtration of the suspension, the presscake is washed with hot water and homogenized with sufficient water to give a 20% paste, which is past 35 times thro a disintegrator (3000 rpm).

Pigmentation by Grinding Production of Beta-CuPc Pigment from Crude CuPc In a kneader , 283kg of crude CuPc is ground for 8 hours with 1131 kg of NaCl and 283 kg of Diethylene Glycol (DEG). Then this paste is boiled in 6000 L of water and filtered using filter press to remove water/soluble substances. Washing with hot water is continued until no water soluble substances can be found. The presscake is then dried at 70 C  – 75 C or using spin flash drier. A intensive greenish blue beta-CuPC is obtained.

Copper phthalocyanine Green The most common organic green pigments are Phthalocyanine green The Phthalogreens are made by halogenating CuPc blue to produce mixtures of CuPc in which many of the 16 hydrogen atoms on CuPc have been replaced by chlorine or mixture of  chlorine and bromine atoms The pigment vary from blue green to yellow green depending on the ratios of bromine to chlorine The yellowish green are obtained with nine to ten bromine atoms per molecule The Phthalogreens are economical and have good light fastness

Copper Phthalocyanine Green 1

The most common organic green pigments are Phthalocyanine green

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The Phthalogreens are made by halogenating CuPc blue to produce mixtures of CuPc in which many of the 16 hydrogen atoms on CuPc have been replaced by chlorine or mixture of  chlorine and bromine atoms

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The pigments vary from blue green to yellow green depending on the ratios of bromine to chlorine

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The yellowish green are obtained with nine to ten bromine atoms per molecule

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The Phthalogreens are economical and have good light fastness

Copper Phthalocyanine Green

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MARKET DEMAND for Copper Phthalocyanine World production of this product is over 110,000 tons/year while the gap between the world demand and the supply according to Business Analyst for Asahi Songwon Colors Ltd for 2011 is 19,000 tons / year. PRODUCTION COUNTRIES Crude CuPc was used to be produced in Japan, Europe and America but now it has been shifted to mainly China and India due to lower labor cost and also mainly as the waste regulations of these countries are not strictly followed.

COST OF RAW MATERIALS USED (Jan 2011)

Phthalic anhydride

$ 1,500 / MT

Cuprous Chloride

$ 6,565 / MT

Urea

$ 350 / MT

Ammonium molybdate

$ 24,000 / MT

CuPc (just raw materials cost)

$ 3,517 / MT

FOB Price of CuPc (from Baiyan China)

$ 5,760 /MT

CALCULATIONS

Material

Weight used for 1 MT CuPc

Unit Price / MT

Cost

CuCl

191 kg

$ 6,565

$ 1,254.00

Phthalic Anhydride

1143 kg

$ 1,500

$ 1,714.50

Urea

1390 kg

$ 350

$ 487.00

Catalyst

2.60 kg

$ 24,000

$ 62.40

Total Cost CuPc

$ 3,517.90 / MT

Profit

The profit for the manufacturers of this product would increase tremendously by using this new process. For example, a medium size manufacturer that produces 5000 MT CuPc/ year with the FOB price of the low quality CuPc is $5.76/kg, the expenses are as follow: If the cost of raw materials ($3.52), packaging ($0.04) and energy ($0.44) to be $4.00/kg then to produce 5000 MT = $20m And if the cost for machinery is assumed to be $1m so a 5 yrs depreciation= $0.2m/yr And if the number of workers employed is 100 with salary assumed to be $600/month each, so salary = $0.72m/yr