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AZO AND COPPER PHTHALOCYANINE PIGMENTS
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PIGMENT
Pigment
• 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.
PIGMENTis a particulate solid dispersed into a medium
without solution or significant interaction
Differences between Pigments and Dyes
Pigments are dispersions in medium but dyes are solutions
Pigments posses particulate properties but dyes do not
Pigments are far more durable and resistant to fading than dye
Differences between Pigments and Dyes
Pigment
Dye
Applications of Pigments
1 Inks : water and solvent based2 Paints : water and solvent based3 Plastics : all types including EVA4 Rubber 5 Glass6 Ceramic7 Textile8 Cement Products9 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
TEST METHOD
• 1.
• TUJUAN : Untuk memastikan bahwa analisa warna plastik resin PVC dengan two roll mill dilakukan dengan benar• • 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. • • 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 130C.• 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.• • Dibuat oleh :•
• • • •
• Pewarnaan Compound I.• Timbang sample = 0,0240 gr .• Tekanan steam dinaikkan menjadi 2,8 – 3,0 kg/cm2 sampai suhu two roll mill menjadi 140C• Setelah suhu two roll mill mencapai 140C, 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.• • 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 diaduk-aduk
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.• • Pressing• Setting alat hot press pada suhu 190C 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 190C 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.• • Formulir Instruksi Kerja :• FIK I5.1-43021/RX Buku harian Analisa Warna Plastik Resin PVC Dengan Two Roll Mill • • • •
Two Roll Mill
Solvent Fastness
Effect of particle size of the pigment
1 Tinting strength2 Gloss3 Viscosity4 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• 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 of di – and tetra – substituted diaminodiphenyls with acetoacetic arylides or pyrazolones
2. The coupling of diazotization of 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 inks & 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 5-acetoacetylaminobenzymidazolone,the second one the coupling components is 5-2-hydroxy-3-naphthoaylamino-benzymidazolone
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 PigmentsYellow (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 Pigments
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 of Pyranthrone Pigments
Anthanthrone Pigments
The only commercial pigments is dibromoanthanthrone which provides shade of scarlet for metallic finishes
They have outstanding weather fastness
Commercial application are in high grade
SYNTHESIS of 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- p-toluidine.Active charcoal is added as clarifying agent and then filtered
Dissolution the coupling componentAcetoAcetanilide, 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, washing to remove salt and drying at 50-55 C. The yield is 700 kg
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.
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)
• 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
Department
Duty
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
1. YieldThe 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.
2.. Environmental EffectMost of the waste of the production of crude CuPc (11,000 tons/yr) is precipitated using Na2S and then is buried underground
Pigmentation Process
Methods Pigments Produced Notes
Dissolving in conc H2SO4 and then sprayed into aqueous solution containing certain additives
Blue Pigment 15:0
Blue Pigment 15:1
Blue Pigment 15:2
Reddish blue pigment with heat stability up to 170 C and poor solvent resistant
Reddish blue pigment with heat stability up to 350 C but poor solvent resistant
Reddish blue pigment with heat stability up to 350 C and good solvent resistant
Grinding with inorganic salts with the aids of polyol solvent in the presence of certain additive in kneader or ball mill
Blue Pigment 15:3
Blue Pigment 15-4
Greenish blue pigment with tendency to agglomerate
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 CuPcCrude 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 3-5 times thro a disintegrator (3000 rpm).
Pigmentation by Grinding
Production of Beta-CuPc Pigment from Crude CuPcIn 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
2 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
3 The pigments vary from blue green to yellow green depending on the ratios of bromine to chlorine
4 The yellowish green are obtained with nine to ten bromine atoms per molecule
5 The Phthalogreens are economical and have good light fastness
Copper Phthalocyanine Green
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
Cuprous Chloride
Urea
Ammonium molybdate
CuPc (just raw materials cost)
FOB Price of CuPc (from Baiyan China)
$ 1,500 / MT
$ 6,565 / MT
$ 350 / MT
$ 24,000 / MT
$ 3,517 / MT
$ 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
Profit
Then Profit :
(5000 MT x $5.76) - $20m - $0.2m - $0.72m + (10% x 5000 MT x $5.76) = $7.88m + $2.88m$10.76m/yr (before depreciation of building, Interest & Tax)
The profit should be more than this as the saving cost for the waste treatment should be added to this amount.