PIGMENT

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

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

Phthalic anhydride , urea , and trichlorobenzene and CuCl with the ratio of 4:12:5:1 are mixed in 1000 L of vessel equipped with an oil bath and stirrer: 2% weight of CuCl 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 max 90%

GLASS LINED PRESSURE REACTOR

ROTARY VACUUM DRYER

Filter Press

Spin Flash Dryer

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 is added quickly to conc. H2SO4 (96%) with ratio of 5-9:1 , 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 water, and the remaining acid is neutralized with K2CO3 and ammonia. After addtion 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 , crude CuPc is ground for 8 hours with NaCl with the ratio 4:1 and with the aid of Diethylene Glycol (DEG).

Then this paste is boiled in water 4x of the total weight 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

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.

Department DutyPurchasing 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

Test method PVC• TUJUAN : Untuk memastikan bahwa analisa warna plastik resin PVC

dengan two roll mill dilakukan dengan benar

• 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.

• BAHAN – BAHAN YANG DIPAKAI:

• PVC Soft Natural (Type : EH 1000)• TiO2 (Type : Tronox CR-834)• DOP (Dioctyl Phthalate)• Stabilizer (Methylene Mercaptide)• Sample

• 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.

• 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.

TWO ROLL MILL

TWO ROLL MILL

GRAVURE VINYL INK TEST METHOD•

• BAHAN – BAHAN YANG DIPAKAI• a) Sampel • b) Vinyl Solution A• c) Vinyl Solution B• d) Toluene• e) Ethtyl Acetate• f) Tinta Putih (PFG 120)• • ALAT – ALAT YANG DIPAKAI• Neraca analitik ketelitian 0,0001 gr• Mixer (Homomixer/IK stiring motor)• Beaker plastik 500 ml• Beaker plastik 100 ml• Pipet ukur 10 ml

• Glass bead 2-3 mm• Pipet tetes• Aluminium foil• Bak pendingin• Saringan 20 mesh• Saringan 2 mm• Zahn cup no.5• Barcoater no.3• Plastik OPP (Oriented Poly Propilene)• Botol sampel plastik 250 ml\• Chromameter

• CARA KERJA • Pembuatan pasta dengan pigment content 10%• Timbang dengan neraca analitik, kedalam beaker plastik 500 ml

berturut-turut.• 72 gram Vinyl Solution A• 18 gram sampel pigment• 40 gram Toluene• 10 gram Ethyl Acetate• Aduk dengan mixer selama 5 menit dengan kecepatan mixer 500

rpm.• Tambahkan 300 gram glass bead yang sudah diayak dan tidak lolos

saringan 2 mm, pasang bak pendingin air pada mixer dan atur jarak daun pengaduk mixer max 1 cm dari dasar beaker plastik

• Tutup beaker plastik dengan menggunakan aluminium foil yang sudah dilubangi (besarnya lubang disesuaikan dengan besarnya batang pengaduk mixer)

• Aduk dengan mixer selama 2,5 jam dengan lecepatan mixer 2000 – 2050 rpm

• Tambahkan vinyl solution B sebanyak 40 gram, aduk dengan mixer selama 5 menit dengan kecepatan 500 rpm.

• Aduk dengan kecepatan 2000 rpm, selama 15 menit.• Saring dengan saringan 20 mesh, untuk memisahkan glass

beadnya.• Ukur viscositas dengan menggunakan zahn cup no. 5• Drawdown pada subtrat plastik OPP

• Draw down Full shade :

• Pigment content 2% dan 7,5% menggunakan barcoater no.3 dengan pengaturan speed barcoater Sebagai berikut :

• Untuk draw down PC 2% speed diatur padda skala 4-5• Untuk draw down PC 7.5% speed diatur pada skala 3,75 • Cara pengenceran pasta pigment 10% untuk pigment content

2%:• Timbang pasta pigment hasil mixer sebanyak 2 gram pada

beaker plastik 100 ml, tambahkan 8 gram vinyl solution B, aduk dengan menggunakan spatulla sampai benar-benar rata.

• Cara pengenceran pasta pigment 10% untuk pigment content 7,5% :

• Timbang pasta pigment hasil mixer sebanyak 7,5% gram pada beaker plastik 100 ml, tambahkan 2,5 gram vinyl solution B, aduk dengan menggunakan spatulla sampai benar-benar rata.

• Draw down Tinting Shade• Timbang 1 gram pasta pigment hasil mixer kedalam

beaker plasti 100 ml, tambahkan 9 gram• tinta putih, aduk dengan spatula hingga rata. Draw down

pada plastik OPP menggunakan barcoater no.3

PAINT TEST METHOD

• TUJUAN : Untuk memastikan bahwa analisa warna solvent based paint dengan long alkyd beckosol P-470-70 dilakukan dengan benar.

• • RUANG LINGKUP : Instruksi kerja ini menjelaskan cara kerja analisa warna

solvent based paint long alkyd beckosol yang berlaku untuk XB-207/I aplikasi solvent based paint untuk pengiriman DIC-Japan atau customer lainnya dengan requirement sejenis.

• BAHAN – BAHAN YANG DIPAKAI

• Long Oil Alkyd Paint Beckosol P-470-70• White spirite / Mineral spirite• TiO2 type CR.838• Co-Dryer

• ALAT – ALAT YANG DIPAKAI• Neraca analitik ketelitian 0,0001 gr• Shaker• Glass bead 2-3 mm• Botol shaker 100 ml• Spatula • Beaker plastik 100 ml• Chromameter• Applicator 6 m• Applicator 10 m• Art paper polos• Art paper bergaris

• CARA KERJA

• Tutup beaker plastik dengan menggunakan aluminium foil yang sudah dilubangi (besarnya lubang disesuaikan dengan besarnya batang pengaduk mixer)

• Aduk dengan mixer selama 2,5 jam dengan lecepatan mixer 2000 – 2050 rpm

• Tambahkan vinyl solution B sebanyak 40 gram, aduk dengan mixer selama 5 menit dengan kecepatan 500 rpm.

• Aduk dengan kecepatan 2000 rpm, selama 15 menit.• Saring dengan saringan 20 mesh, untuk memisahkan glass

beadnya.• Ukur viscositas dengan menggunakan zahn cup no. 5• Drawdown pada subtrat plastik OPP

• Draw down Full shade :

• Pigment content 2% dan 7,5% menggunakan barcoater no.3 dengan pengaturan speed barcoater Sebagai berikut :

• Untuk draw down PC 2% speed diatur padda skala 4-5• Untuk draw down PC 7,5% speed diatur pada skala 3,75 • Cara pengenceran pasta pigment 10% untuk pigment content 2%:

• Timbang pasta pigment hasil mixer sebanyak 2 gram pada beaker plastik 100 ml, tambahkan 8 gram vinyl solution B, aduk dengan menggunakan spatulla sampai benar-benar rata.

• Cara pengenceran pasta pigment 10% untuk pigment content 7,5% :• Timbang pasta pigment hasil mixer sebanyak 7,5% gram pada beaker plastik 100 ml,

tambahkan 2,5 gram vinyl solution B, aduk dengan menggunakan spatulla sampai benar-benar rata.

• Draw down Tinting Shade

• Timbang 1 gram pasta pigment hasil mixer kedalam beaker plasti 100 ml, tambahkan 9 gram tinta putih, aduk dengan spatula hingga rata. Draw down pada plastik OPP menggunakan barcoater no.3