Crosslinker for exterior durable Polyester powder coatingslitmuschem.com/data/admin/board_upload/4/files/35f6367a8254bfb... · Crosslinker for exterior durable Polyester powder

- 1 - PCA-501

PCA-501

Crosslinker for exterior durable Polyester powder coatings

Applied Chemicals Division, Litmus Chemical Co.,Ltd. 765 Sansingi-ri, Illo-eup, Muan-gun, Jeollanam-do, Korea

Telephone: +82 61 283 3305 Fax: +82 61 283 6605 e-mail: [email protected]

- 2 - PCA-501

1. Introduction 1.1 Crosslinker for exterior durable Polyester powder coatings

Powder coating compositions formulated with a polyester polymer are especially useful for their

corrosion resistance and exterior durability. Powder coating compositions including a carboxylic

acid-functional polyester and triglycidyl isocyanurate (TGIC) as a curing agent are common.

Although these powder coating compositions give useful coatings with good properties, they are

expensive to formulate because of the cost of the TGIC. Also, TGIC presents the formulation with a

toxicity problem and requires relatively high cure temperatures of from about 200℃.

In accordance with PCA-501, a thermosetting powder coating composition is provided.

The composition comprises a carboxylic acid group-containing polyester having a Tg of from about

30℃ to about 85℃, and an acid number of from about 20 to about 80, and a polyhydroxyalkylamide

curing agent (PCA-501).

The powder coating compositions of PCA-501 cure at significantly lower temperatures than

compositions with TGIC and give resultant coatings with good exterior durability plus a good blend of

other physical properties such as appearance, hardness, impact resistance and chemical resistance.

1.2 The Structure of PCA501

(CH2)n[CON((CH2)m(OH)) 2] 2

n= 2-4 , m = 2-10

M.P=110-130 DEG C

- 3 - PCA-501

Information Sheet

PCA-501

L i t m u s Chemical


Description PCA-501 is a curing agent suitable for the production of exterior durable polyester powder coatings. It has the characteristics of low toxicity, no irritant to skin, good weather durability etc. The chemical structure of PCA-501 is polyhydroxyalkylamide.

Typical Properties Aspect white granular solid Melting Point 120 ~ 128℃ Volatile max.1.0 Hydroxy value 650 – 750 mgKOH/g Bulk-Density approx. 0.7 g/cm3 Cure schedule 8 minutes @ 200℃(metal temperature) 10 minutes @ 180℃(metal temperature) 20 minutes @ 165℃(metal temperature) Use level ~ 15 PHR (Part per Hundred Resin) Packing Available in 20 kg net weight, non returnable polyethylene bags.

- 4 - PCA-501

Shelf Life Store under cool, dry conditions. It is recommended that the material be used within 12 months of certification. Handling Avoid contact with skin & eyes & wear appropriate dust mask. Futher details can be obtained from the relevant Health & Safety Data Sheet.

- 5 - PCA-501

Information Sheet

PCA-501



STARTING FORMULA

Polyester Powder Coatings for full-gloss,white

Polyester Resin (AV=33~35)

PCA-501 Leveling Agent

Benzoin TiO2-R706

95 5.1 1 0.5 60

Test Result

Item Procedures Test Method Result

Surface Appearance ASTM D523 Visual Observations Uniform

Coating Color ASTM D2244 Visual Observations White Gloss BS3900:D5 60 deg >90%

Thickness ASTM D1186 D.F.T Guage 60-80 ㎛

Elasticity ASTM D522 Cylindrical Mandrel φ 8㎜×180˚ No Crack

Impact Strength ASTM D2794 Dupont Impact tester ≥ 1000g/50cm

Adhesion ASTM D3359 Cross Hatch Cutting Device & Tape 100/100 (1㎜×1㎜)

Overbake Resistance ASTM D2454 210℃×1hr Δ E≤ 1.5

Salt Spray Resistance ASTM B117 5% Salt @100℉(1/16"max.

undercutting 1500 hours exposure)

No Blister

- 6 - PCA-501

Information Sheet

PCA-501



STARTING FORMULA

Polyester Powder Coatings for full-gloss,white

UCB CC7630 (AV=33~35)

PCA-501 Leveling Agent

Benzoin TiO2-R706

95 5.1 1 0.5 60

Test Result

Item Procedures Test Method Result

Surface Appearance ASTM D523 Visual Observations Uniform

Coating Color ASTM D2244 Visual Observations White Gloss BS3900:D5 60 deg >95%

Thickness ASTM D1186 D.F.T Guage 60-80 ㎛

Elasticity ASTM D522 Cylindrical Mandrel φ 8㎜×180˚ No Crack

Impact Strength ASTM D2794 Dupont Impact tester ≥ 1000g/50cm

Adhesion ASTM D3359 Cross Hatch Cutting Device & Tape 100/100 (1㎜×1㎜)

Overbake Resistance ASTM D2454 210℃×1hr Δ E≤ 1.5

Salt Spray Resistance ASTM B117 5% Salt @100℉(1/16"max.

undercutting 1500 hours exposure)

No Blister

- 7 - PCA-501

Information Sheet

PCA-501



STARTING FORMULA

Polyester Powder Coatings for full gloss finish, white

UCB CC7630 UCB CC450

PCA-501 TGIC(GOJAE) Leveling Agent

Benzoin TiO2-R706

PCA-501

95 -

5.1 - 1 0.5 60

TGIC

- 93 -

7 1 0.5 60

Test Result

Item Procedures Test Method PCA-501 TGIC

Surface Appearance ASTM D523 Visual Observations Uniform Uniform

Levelling Visual Observations Uniform Uniform Surface Defect Pinhole, fish eye, crater No defect No defect

Gloss BS3900:D5 60 deg 95% 95% Thickness ASTM D1186 D.F.T Guage 60-80 ㎛ 60-80 ㎛

Elasticity ASTM D522 Cylindrical Mandrel φ 8㎜×180˚ No Crack No Crack

Impact Strength ASTM D2794 Dupont Impact tester ≥ 500g/50cm ≥ 500g/50cm

Adhesion ASTM D3359 Cross Hatch Cutting Device & Tape 100/100 (1㎜×1㎜) 100/100 (1㎜×1㎜)

Overbake Resistance ASTM D2454 210℃×1hr Δ E≤ 1.5 Δ E≤ 1.0

Alkali Resistance ASTM D1308 10% NaOH × 24hrs No Blister No Blister

Acid Resistance ASTM D1308 10% H2SO4 × 24hrs No Blister No Blister

0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200 1400 1600 1800 2000

Gloss(60deg)

Hours

Accelerated Exposure Weather-Ometer (ASTM G53-88)

#061112 CC7630/PCA-501

Polyester Resins for PCA-501

Producer Trade Name Product Types

UCB Chemicals Crylcoat

491, 810, 7642, D 8183, 632, D8255, 7622, D 8213, 7602, 7617, 7630, 7631, 7624, D 8059, 7641/43, 7640, D 8306, D 36 342

DSM Resins Uralac

P 855, P 875, P 846, P 860, P 800, P 6103, P 870, P 865, P 879, P 833, P 835, P 805, P 812, P 815, P 862, P 867, P 818, P 7400

Solutia [ ex) Höchst / Vianova ]

Alftalat AN 995, AN 989, VAN 9959, VAN 9942, 03548, 03629, 03728, 03807, VAN 9882

McWorther [ ex) ICS / Syntech ]

Albester 5140, 5540, 5550, 5580, 5590, 6530, 5544, 5501, 6580, 6520

Cray Valley [ ex) Resisa ]

Reafree 8180, 8300, 8500, 8580, 8585, 8780

Sir Industriales S.p.A. Sirales PE 7820, PE 7810, PE 7809

Scott Bader Ltd. Texicote 1095, 1195, PD 9206

Bayer ( Ruco Polymer ) Rucote 915, 911, XP- 5600, 914, 945

Chan Sieh Ltd. Kuotex EL 8300, EL 8800, EL 8400, EL 8500

Synthopol GmbH Synthalat S 8400, S 8500, SP 561, SP 840, SP 679

Dic / Reichhold Fineclad M 8961, M 8962, M 8790

Litmus Chemical Co., Ltd.

Surface optimizing product for PES/PCA-501 powder coating

Resiflow PV 88 Resiflow CP 77 BYK 364P/360P Powdermate 570 486CFL/505PFL

Additol XL-496 Additol VXL9820 Perenol F 30P Modarez MFP-B Flow agent

Modaflow3 Modaflow 2000 Benzoin Thixin E/R Add 902/904 Crayvallac PC

Degassing agent Pisparlon PSJ-8528 Modarez SI 29-079

Powdermate 542DG

Surfynol P200

Martinal OL-111 Socal U-1 Alcan SF Portaryte Degassing filler Ceraflour 961 Ceraflour 993 Ceridust 9615 A Ceridust 3910

Lanco PP 1362 P Vestowax A 616 Lanco 1394 F Deuteron MPO Waxes (Matting) Ceraflour 990 Wax MPP 620 F Licowax C Lanco TF 1778

Tinuvin 144 Chimassorb 119T Uvinul Tinuvin 111FD Light

Stabilizer Tinuvin 622LD Tinuvin 928 (Tin 622/Chim

119)

Irganox 1010 Irganox B

225(1010/168) Irganox 1076 Irganox 1035

Irganox B 921(1076/168)

Irgafos 38 Irgafos 168 Irganox 490 Heat

stabilizer Irgafos XP 40

(P-EPQ/HP-136)

Tribo additives

Tinuvin 144 Texaquart 900 Crylcoat 150 Tinuvin 111FD

Cab-O-Sil Tixogel Aerosil Deuteron PMH Fluid agent

Ceridust 9630 Ceridust 9205 Lanco TF 1778 Ceraflour 920 Wetting

dispersing agent

Ceridust 5551 K-Sperse XD-6201

Deuteron PO 100 Ceraflour 960


TEST REPORT 2006.11.21

1. 제 목 : PCA-501 (리트머스화학(주)) 과 T105 Curing Agent 남해화학(중국産) 신규원료검토

2. 배 경 :

현재 분체도료에 사용되고 있는 T105경화제를 PCA-501로 대체하여 물성비교 및

대체가능성을 검토하여 적용코저함.

Product Name PCA-501 T105 Manufacturer Litmus Chemical Co.,Ltd. South sea chemical

Chemical Composition HYDROXYALKYL AMIDE (Bis(N,N’-Dihydroxyethyl)-Adipamide)

Hydroxyl equivalent 82-86 78-82 Epoxy equivalent - - Viscosity at 120℃ - -

Melting range 120-125℃ 125-129℃ Solid content Min 0.6(moisture) 99% 이상

Chlorine content - - Molecular Weight - -

Appearance Powder or granule Powder or granule 특 징 NON TOXIC LOWER TOXICITY

3. 실험 방법/비교항목 :

1) 제조방법: 배합 – Premixing (1분) – ZSK-30분산(2회분산) – 분쇄(140 mesh Filter) – 도장 및 경화.

2) 배합은 동일배합에서 경화제만 대체변경 제조하여 외관 및 물성등을 비교함.

3) 4종의 도료를 각각 제조후 조건별 혼용시 외관 및 LEVELLING비교(혼용성 비교)

4) 외관 및 1차물성이 양호할 경우 장기물성 및 전항목 물성검사 필요함.

4. 적용배합 : PX8576-WHITE(기준) – ㈜케이씨씨(한국)

* PCA-501 / T105와 비교시

FORMULA 기준(STD) 동량대치(T105) 비 고 Polyester(CC7630) 95 95

PCA-501 5.0 - T105 - 5.0

Flowing agent(PV-5) 1.0 1.0 BENZOIN 1.0 1.0 PE1544 1.0 1.0

TiO2 55 55 BaSO4 5 5

5. 시험 결과 :

* PCA-501 / T105와 비교시

시험항목 자사제품(PCA-501) 동량대치(T105) 비 고 외 관 양 호 Hazy현상있슴 색상비교 S T D 1.32 T105사용시 Yellowing 심함

Gel time(200℃) Levelling 양 호 떨어짐

Gloss(60o) 95% 94% Bending(1/8”) 양 호 양 호

Erichsen Test(6mm) 8mm 8mm Impact

Resistance(1kg/50cm) 1kg / 50cm 1kg / 50cm

Adhesion(100/100) 100/100(1mm) 100/100(1mm) 내열성(200℃ x 1hr) 0.88 1.5 색차비교

5% NaOH x 24hr 미시험 미시험 비등수후 2차물성

Impact Resistance(500gr/30cm) 1kg/50cm 1kg/50cm

Erichsen Test(6mm) 6mm 6mm Cross cut 100/100 100/100

조건별 혼용성 시험결과(자사제품(PCA-501)과 비교)

조 건 / 혼 용 성 Gloss(60o) 외 관 Remark

기존(50%)/T105(50%) 혼용시 92%

HAZY현상있슴, PINHOLE

(120㎛이상) LEVELLING떨어짐

기존(99%)/T105(1%) 혼용시 95% 양 호 1% 상당제품 혼합시 외관

기존(1%)/T105(99%) 혼용시 92% HAZY현상있슴 1% 상당제품 혼합시 외관

6. 결론 및 의견 :

* 자사제품 PCA-501/ T105와 비교시험결과,

1) T105경화제를 사용한 도료는 도막외관이 HAZY함.

2) T105경화제를 사용한 도료가 내열성이 취약함.

3) 기계적 물성은 동등수준임(내충격성,BENDING,ERICHSEN)

Measuring the Reaction Kinetics of Polyester/PCA-501(HAA) Powder Coatings With Dielectric Analysis (DEA) Dr. Georgi Beschiaschvili and Liselotte Tanner; and Manfred Wenzler, November 6, 2003

Figure 1a Differential Scanning Calorimetry

Isothermal Cross-linking of Copolyester/TGIC at 165℃

Thermosetting powder coatings only achieve optimal properties after they are completely cured. The

degree of cure is important because it influences the mechanical properties, the corrosion resistance and

weathering resistance of the final powder coating. Knowledge of the reaction rate and reaction kinetics is

therefore of significant practical use. For typical thermosetting materials, the chemical reaction taking

place during cross-linking is exothermic, and the reaction can be followed using differential scanning

calorimetry (DSC).

Figure 1b Dielectric Analysis

Isothermal Cross-linking of Copolyester/TGIC at 165℃

The enthalpy of reaction for the cross-linking of PCA-501(HAA) with carboxyl polyester is very low. It is

not possible to determine the progress of this reaction using DSC techniques. Until recently this was a

handicap. Determination of the degree of cure was only possible by measuring the development of the

mechanical properties of PCA-501(HAA) coatings—for example, slow penetration and impact resistance.

In comparison to DSC methods, the accuracy of measuring mechanical properties is very poor and not at

all suitable for coatings of limited flexibility, such as super-durable polyester powder coatings.

Dielectric analysis (DEA) has been used since the mid 1930s for the analysis of various polymeric

materials. In the last few years, DEA has been used increasingly for epoxy resin systems.

Figure 2 DSC vs.DEA

Degree of Conversion:Copolyester/TGIC PowderCoatings

In this study, the reaction kinetics and the overall thermodynamics of copolyester/PCA-501(HAA) cross-

linking were investigated by using DEA. The use of DEA for char-acterising the reaction kinetics of PCA-

501(HAA) powder coatings was verified by conducting comparison measurements on a

polyester/triglycidylisocyanurate (TGIC) powder coating using both DEA and DSC techniques.

Material and Apparatus

· PCA-501 (Bis-N,N-Dihydroxyethyladipamide)

· Carboxyl polyester with acid value 30, UCB Chemicals

· Polyester/TGIC and polyester/PCA-501 powder coatings

· Dielectrometer TA 2970, TA Instruments GmbH

· Differential Scanning Calorimeter, Polymer Laboratories

Method

The powder coating sample was applied to the sensor with a spatula at room temperature. The coated

sensor was then placed in the DEA kiln and raised quickly to the required temperature (within

approximately 5 minutes). The resulting cross-linking reaction was investigated at dif-ferent

temperatures using a ceramic single-surface sensor isotherm. The measurements were made under a

nitrogen atmosphere.

Dielectric Analysis

Figure 3 Dielectric Analysis

Isothermal Cross-linking of Copolyester/PCA-501(HAA) at 150℃ and 200℃

With Dielectric Analysis the real component e' and the imaginary component e" of the complex dielectric

constant e*= e’ - ie” are determined in relationship to temperature and the frequency of the alternating

electric field. The real component e' is proportional to the reversible stored energy, and the imaginary

component (or loss factor) e" is proportional to the dissipated energy resulting from the rotation of polar

groups.

The PCA-501(HAA) cross-linking reaction was traced by following the ionic conductivity s:s = e" 2P f eo

where f is the frequency in Hz of the alternating electric field and eo is the dielectric constant (8.85*10-

12 F/m).

Ionic conductivity results from the presence of ionic impurities in the system (e.g. inorganic and organic

salts) and is dependent on the viscosity of the sample. If the concentration of the ionic impurities

remains constant during the cross-linking reaction, the ionic conductivity makes an ideal parameter for

following the changes in viscosity that occur during crosslinking (1). Starting with an uncured powder

coating, the ionic conductivity increases rapidly with increasing temperature, as the powder first sinters

and then melts. With the onset of cross-linking, the viscosity of the powder coating increases with a

resulting parallel decrease in ionic conductivity. This process continues until the reaction is complete and

the coating fully cured. The change in ionic conductivity during the isothermal cross-linking reaction is

used to determine the degree of conversion a as a function of time.

The loss factor e" is composed of two components:

e" = s/2P f e0 + e"d where e"d is the component of the loss factor e" caused by dipole relaxation losses.

If DEA measurements are made at low frequency, under these conditions, the dipole relaxation

component e"d is negligible and the loss factor e" is de-termined completely by the ionic conductivity

(2,3). Results of Copolyester/TGIC Cross-linking Figures 1a and 1b illustrate the isothermal cross-linking

of copolyester/TGIC as measured with DSC and with DEA at 165°C. With DSC the change in enthalpy

was recorded, whereby with DEA the change in ionic conductivity was measured. Control measurements

were made on the copolyester resin without cross-linker.

The degree of conversion measured as a function of time by DSC is given by Equation 1:


Degree of Conversion: Copolyester/PCA-501(HAA) Powder Coatings

a (t) = H(t)/H0 where H(t) is the reaction enthalpy as a function of time and H0 is the total reaction

enthalpy.

A very good correlation between DSC and DEA is achieved if the degree of conversion measured against

time by DEA is calculated using Equation 2: a (t) = {s(0)- s(t)}/{ s(0)- s(`)} where s(t), s(0) and s(`)

are the corresponding values of ionic conductivity at a time (t), at the beginning of the reaction (0) and

at the end of the reaction (`).

From a comparison of the two results (Figure 2), it can be seen that the two curves are very similar.

Taking into account the accuracy of the two test methods, the curves can be considered virtually

identical. This indicates a very good correlation between the two analytical techniques. The proposed

process to determine the conversion curve of the cross-linking reaction from DEA measurements

(Equation 2) assumes a linear relationship between the ionic conductivity s and the degree of conversion

a.

The functional relationship between the degree of conversion and the ionic conductivity s is given in the

literature by Equation 3: a = k log s + C (where k and C are constants) (4). Very good correlation has

been observed between the DEA and DSC techniques based on a linear relationship between the ionic

conductivity and degree of conversion.

Results of Copolyester/PCA-501(HAA) Cross-linking


Determination of the Kinetic Parameters(k & n)

The changes in ionic conductivity with isothermal cross-linking of the PCA-501 powder coatings at two

different temperatures, 150°C and 200°C, are shown in Figure 3. The conversion curves of the PCA-

501(HAA) cross-linking reaction at three different temperatures, as calculated using Equation 2, are

shown in Figure 4. At 200°C, 99% conversion is reached after 5 minutes, whereas at 150°C the

conversion after 5 minutes is only 68%.

The reaction profile of the powder coating cross-linking is represented by the following nth order kinetic

Equation 4: da(t)/dt = k{1-a(t)} whereby, da(t)/dt is the reaction rate, n is the order of the reaction

and k the appropriate rate constant. The rate constant is dependent on temperature as given by the

relationship (Arrhenius Equation 5) k = A exp (-Ea/RT)

The kinetic parameters, namely the pre-exponential factor (A) and the activation energy (Ea), could be

determined by plotting Ln (k) against the reciprocal of the absolute temperature (1/T).

The rate constant k and the reaction order were determined by plotting log (da(t)/dt) against log (1-

a(t)). The resulting curve was a straight line with a gradient n. The corresponding rate constant could

then be determined by extrapolating log (1-a(t)) to zero.

The plots of log (da(t)/dt) against log (1-a(t)) for three temperatures are illustrated in Figure 5. The

plotted values for the different temperatures lie on parallel gradients, thus confirming the validity of the

proposed kinetic equations (Equations 4 and 5). The gradients of all three lines gave a reaction order

n=1.4. Having determined the reaction rate, both the activation energy (Ea) and the pre-exponential

factor could be estimated using the Arrhenius equation and the plot of ln k against 1/T. The results of

the kinetic analysis were as given in Table 1.

Conclusion

The reaction kinetics of polyester/ PCA-501(HAA) was investigated by monitoring changes in ionic

conductivity, with the ionic conductivity being directly influenced by the viscosity of the system. During

cross-linking the viscosity of the coating increases resulting in a corresponding decrease in ionic

conductivity.

Comparative tests made with a polyester/TGIC powder coating using both DSC and DEA techniques

resulted in a very good correlation between the two techniques. The results depicted in Figures 2 and 3

prove that DEA is a suitable method for assessing the conversion rate of polyester/PCA-501 powder

coatings.

DEA provides an accurate and reproducible method for measuring the reaction kinetics of polyester/

PCA-501(HAA) powder coatings. From the results of DEA, precise predictions about the required curing

conditions (i.e. time and temperature) can be made.

References

1. N.T. Smith and D.D. Shepard, European Coatings Journal, 930-935, (1995)

2. D.R. Day, Polymer Engineering and Science, 29, 334-338, (1989)

3. K.A. Nass and J.C. Seferis, Polymer Engineering and Science, 29, 315-324,

(1989)

4. R.H. Kienle and H.H. Race, Trans. Elektrochem. Soc., 65, 87 (1934)

单螺杆挤压机和双螺杆挤压机的比较 I


粉末研究部

12

SINGLE SCREW EXTRUDER vs. TWIN SCREW EXTRUDER 单螺杆挤压机和双螺杆挤压机比较

EXTRUDER TYPE

挤压机种类

Reciprocation Single Screw单螺杆 Intermeshing Co-rotating Twin Screw双螺杆

SCREW SHAPE Broken by 3 Gaps & Pins

2 Flight (加工 EMC采用 3 Flight)

COMPANY Buss Krrup Werner & Pfeiderer

TECHNICAL COUNSELOR Elmer Wiedemann (Process Engineer) Dieter Hess (Business Manager, Heat & Shear Sensitive Products)

DATE 2004. 10. 25 2004. 10. 13

1

CHARACTERISTICS 1. High Screw Speed

2. Great L/D Ratio

a. 7~8 L/D → 11 L/D

b. 特别加工 Acrylic clear时用 17 L/D

3. Side Feeding System

4. New Screw Shape & configuration

DG Screw

D Screw (Europe的粉末涂料生产企业正在使用)

DV Screw (New Screw)

为了不需要再分散操作，提高产品的质量、生产效率、Homogeneity，介绍现有的 Super

Compounder(SC)中介绍 MEGA Compounder(MC)的 ZSK。

*MC Technology ① High/highest Screw Speed ② Great L/D Ratio (现有的 SC是 4Barrels，MC是 5Barrels) ③ New Screw Configuration ④ Improved Wear Protection 现有的 Super Compounder 中更换成 MEGA Compounder ZSK 的时候， Maintenance(磨损比现在略微严重)，能源消耗增加，Throughput Rate 增加，最终制造成本大约下降 40%。

2

FEEDING ACEPTANCE 1. 为了抑制胶化、提高喂料能力，在D螺杆排 Zone中间的第一

个螺杆的飞轮之间的角度从 30o变为 110o。

2. 需要根据喂料的原料的特点变更螺杆的尺寸

① Fine Powder Feeding : 缩小螺杆飞

② Coarse Powder Feeding : 加大螺杆

3. 为了提高喂料能力，改变 Hopper。

Open Hopper(ELT) : 现在的 KCC系统

↓

Hopper with Screw(ELS) : 过去的 PLK系

↓

双螺杆 Side Feeder(DSH) : New PCS Sy

为了提高 Fine Powder的喂料能力，介绍两种螺杆

① 单螺杆 Flight Screw ② Undercut Profile Screw

*客户的应用案例(客户和螺杆的种类未确认)

Screw rpm Amount of Fine Powder(12μm) Throughput Rate(kg/h)

900 0% 900

900 5% 1000

900 50% 500

600~900 100% 150~200

中，喂料区和Kneading

之后螺杆的角度是 30o。

。

轮和 Liner之间的间隔

飞轮和 Liner之间的间隔

统

stem

3

RESIDENCE TIME D Screw (7~8L/D)

(正在对上述结果进行再次确认)

螺杆 rpm越大停留时间越短。

*ZSK 40 (5Barrels, Polyester)

Screw rpm Residence Time(sec) Throughput Rate(kg/h)

300 15~20 100~200

600 8~14 200~400

900 4.5~7 400~600

挤压机 Screw rpm Residence Time

/Diameter(sec/D)

Residence Time

(sec)

Throughput

Rate(kg/h)

PCS-30 400 0.8/D 24

-46 400 0.8/D 36.8

-55 400 0.9/D 49.5 250

-70 400 1.0/D 70

-100 400 1.1/D 110

-140 400 1.4/D 196 2500

4

RESIDENCE TIME DISTRIBUTION 虽然认为停留时间的分布与双螺杆挤压机相同，但是没有具体数据证实。

ZSK

APV

Buss

Indicator Amount

Residence Time

对此没有具体的数据 (WP的意见)

SHEAR DEAD ZONE 没有死角，但是飞轮和 Liner之间的缝隙随着挤压机 Diameter的增加而加宽。

No Dead Corners

PRE-MIXING EFFECT 需要根据喂料的原料特点改变 Hopper的喂料螺杆。例如，New Hardener System : 预

搅拌的粉末的大小重要。

对此，难以总结一般性的倾向，需要根据各公司的原料的特点决定。

与挤压机类型无关，是非常重要的部分。

WP推荐使用MIXACO。

挤压机 46 100 140

Shear Gap 0.6mm 0.8mm 2.0mm

5

挤压机 Type SC MC

Screw rpm 300 900

(ZSK25： 1200)

Throughput Rate of ZSK-40 (kg/h) Avg. 200 Avg. 400~500

挤压机 Type WP

ZSK40

AVP

2040PC

Buss

PCS70

Motor Power (kw) 66 26 46

Screw rpm 900 750 500

L/D 20 17.5 7

Max. Throughput Rate (kg/h) 620 350 550

OPERATION SPEED & THROUGHPUT RATE 1. 将传统的 PLK System 变更为 PCS System 时，Screw rpm 由 200~300 增加到

500~600.

2. DG Screw向 DV Screw转换， Throughput Rate增加 50%.

1. 双螺杆挤压机上 Operation Speed和 Throughput Rate具有比例关系.

2. Buss 挤压机是相对比脚手架（scaffolding ）低。.

3. 即便是 Barrel Length(4 or 5 Block), Screw rpm增加，当制造 Polyester/Primid or

PT910 时，对 Gel Time或 Surface Quality完全无影响.

4. Screw rpm 增加将导致 Throughput Rate 增加，高温下制造 TGIC-free Type

Powder，提高 Surface Quality.

OPERATION TEMPERATURE 通常将 Screw, Barrel 的 1’st Zone Temp.提高维持在 Barrel 的 2’nd Zone(吐出部位)

Temp.的 1/2.

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PROCESS LENGTH (BARREL LENGTH)

实验结果

1. D Screw和 DV Screw 变更无差异.

2. Barrel Length对 Quality有较大影响.

(*Akzo Novel的 Quality 评价标准，越接近 ‘1，越是 Good Quality)

按照上述结果，认为 Buss Engineer将会依组合不同，根据 Screw Type显示出较大差

异.

1. WP 挤压机与 Buss相比，具有 2倍以上的 Process Length(L/D).

2. Process Length和Gelation Effect无相关关系. 特别是 Residence Time变短, Time

Distribution也会变窄，因此，Temp. Control等如果没有出错的话，就没有 Gelling

Effect.

WEAR SENSITIVITY 1. 如 Table所示，如果产生磨损，应该更换 Part.

2. 通常，提高 Screw rpm程度至 Flight和 Liner之间产生的 Gap那样进行制造。.

1. 由于是 High Screw Speed，使用可耐高强度磨损的材料. 2. 如下情况例外：为了提高 Fine Powder的 Feeding，如果使用单螺杆 Flight

Screw，与 Standard Screw相比，显示为约 75%的耐磨性.

挤压机

PCS-55

Screw rpm Feeder rpm Throughput Rate(kg/h) Quality*

11 L/D 500 280 450 1.6

8 L/D 500 150 250 2.4

Flight Wear Pin Wear 挤压机

Height Width Width

46 1mm 0.5mm 0.4mm

70 1mm 1.0mm 0.6mm

100 2.5mm 1.2mm 1mm

7

SCALE UP M1 / M2 = ( D1 / D2 )x

M1, M2 : Throughput of Buss Kneader 1 & 2

D1, D2 : Screw Diameter

x : exponent ranges between 2 & 3

Scale Up Volume Factor

即，在同一条件下，投入量等于 ZSK-25 的投入量乘以上述 Factor。

OTHERS 1. 制造时，向挤压机投入的 Pre-mixed Powder量只有能填满挤压机空间就行，不要让

粉末填满与挤压机连接的 Hopper.

2. 将 Motor的 Specific Energy调节为 0.04~0.06 kw h/kg.

3. PVC Cleaning时，将 Screw和Barrel Temp.维持在 100~110oC后，投入 PVC， PVC

Melting后将温度降低.

挤压机的性能分为 Distribution, Dispersion予以说明： 1. Distribution是指 Buss或 WP的挤压机同一(个人意见： Buss 挤压机更有优势. WP的技术人员也认为对这个部分 Buss 挤压机并不逊色。)

2. Dispersion是指WP 挤压机更有优势.

ZSK-40 ZSK-50 ZSK-58 ZSK-70

ZSK-25 1.00 8.00 12.49 21.95

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PROBLEMS IN PRACTICE PCA-501(Hydroxyalkyamide)-based Powder Coatings 制造条件

1. Higher Residence Time – Reduced Output (不要过满地填充挤压机内空间，投入

Pre-mixed Powder.)

2. Higher Shear Rate – Maximum Screw Speed

3. Higher Temp. –

4.使用 D & DV Screw.

制造时 Batch更换或最后 Batch时发生 Hazy现象. 对此意见如下： 1. Ciba和其他欧洲的粉末制造企业出现的现象与 KCC现象不同。即在 KCC出现部分的 Hazy现象，而在欧洲企业制造全过程都出现。因此改变制造条件 (温度, Screw 排列, 速度…) Hazy现象就会消失.

2. 认为 KCC的现象的出现，与挤压机自身制造条件相比，更有可能是 Feeding的问题.

3. Volumetric Feeder 并非为每小时的定量投入. 根据 Hopper 内累积的Pre-mixed Powder 量多少，投入量发生变化，因此当更换 Batch 或最后Batch时投入量发生变更，不能维持合适的 Torque，由此出现 Hazy现象。 –推荐 Gravitic Feeder.

4. 尽可能缩小 Feeder和挤压机投入口的距离 (0.5~1m). 5. Pre-mixing时，最好在 Mixing Container填至 75%时进行 Mixing. 6. WP进行的制造实例

挤压机 Screw rpm Temp.(oC) Powder Type

80/100/100 Hybrid, TGICZSK-58 900

90/110~120 PT910, Primid

Screw & Zone 1 Zone 2 (吐出部)

Temp. 40~50oC 100~120oC

9

Acrylic-based Powder Coatings 使用 Long Barrel 挤压机 (17L/D).

用传统的 7~11 L/D 挤压机不能制造.

与传统的挤压机相比有很多不同，在此省略。现在正在使用 Long Barrel 挤压机.

Fast Curable Powder Coatings 1. DG Screw & D Screw

2. 提高 Temp.时降低 Screw rpm，使用 Die的 Hole Size大的.

制造上无问题，但没有拿到详细的制造条件.

High Filler Loading EMC DG Screw

当 EMC在Melt State开始出来，降低 Temp.

Buss也为 EMC企业供应挤压机，因此可以提供与 EMC制造相关的技术。

为 EMC 企业供应约 4台，因此并无这方面的技术信息。

Screw Zone 1 Zone 2 (吐出部)

Temp. < 50oC < 50oC < 50oC

Screw Zone 1 Zone 2 (吐出部)

Temp. 100 ~ 120oC

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DISCUSSION 1. 现在挤压机变化趋势都相同

a. Long Barrel Length

b. High Screw Speed – High Throughput Rate

c. High Temp.

2. 应用 Buss的挤压机可制造粉末涂料和 EMC 制造，可以得到这方面的信息，但是 WP的挤压机适合于制造粉末涂料，但不适合 EMC 制造，难以获得信息.

3. 认为 Fast Curable Powder Coatings (for Rebar & Pipe)制造时 Buss 挤压机更有利.

4. 究竟是哪一种机型绝对更优，恐怕难以下结论。必须与生产部门一起，在改变 Screw Arrangement, Shape, Temp.等条件下进行不同的实验。特别是对于 Buss 挤压机的性能

人们尚无充分的理解.

5. 与要求大量连续生产的产品相适合的挤压机生产效率等相关课题，需要今后进行更多的研究.

6. 现在对于 Buss单螺杆挤压机按 Screw Type进行的分散性和 Process Window实验已经得到了验证。但对于 KWP(ZSK Series)，由于实验所需的 Powder没有及时到达，双

螺杆挤压机的比较研究尚未结束. 一旦收到 KWP最新机型制造的 Powder，将立即进行性质评价，编写报告书.

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15

单螺杆挤压机和双螺杆挤压机的比较 II -使用 RPT-3000进行的分散性和 Process Window分析-


粉末研究部

1

各类型挤压机的性能比较实验

1. 背景迄今为止，对各类型挤压机，特别是往复单螺杆和双螺杆挤压机的性能进行的体系的研究还很不充分，各挤压机的条件(Screw Type, Arrangement, Speed, Screw & Barrel Temp., Barrel Length etc)各不相同，各种应用的方案的研究也不充分，在此状态下，对各种制造条件下产品生产和粉末涂料性质的改善和改良进行了实验。这个基础实验对挤压机性能的基础研究和组合特点，提出适当的制造条件，将对降低大量生产时的不合格率、提高质量具有重要意义。 2. 目的前面的报告“单螺杆挤压机和双螺杆挤压机的比较 I”中整理了各仪器的参数和各公司提供的信息，本报告根据制造实验对往复单螺杆挤压机和双螺杆挤压机的性能和特点进行分析。一般来说，研究挤压机性能时，需要研究以下三个方面内容： ← 分散性(Distribution & Dispersion) : ↑ Process Window(工艺的稳定性) : 挤压机运转条件的变化引起的产品性质的变化程度越小，越可以实现稳定的生产。 → 生产效率其中，生产效率通过实验室阶段的小量制造实验难以证实，所以只有通过分散性和 Process Window的比较研究。还需要以后对生产效率进行研究。

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3. 实验方法

3.1. 组合 Type PCA-501 based Powder

Coating Fast-curable Powder Coating

Name PX4324 EX4411 Resin CC7630 95.0 CNE00105 100.0Hardener PCA-501

(hydroxyalkyamide)

5.0 MIA-5 Casamid783

5.01.0

Pigment CR-80 GN9500 Bayferrox420

50.00.20.2

CR-80 GN9500 Bayferrox420

5.00.11.5

Additive PV-5 Benzoin PE1544

1.00.50.5

PV-5 Benzoin

1.00.5

Formulation

Extender BaSO4 10.0 BaSO4 15.0 3.2. 挤压机

3.2.1. 往复单螺杆挤压机 : Buss PLK-46

DG Screw

DV Screw

Screw (WK)

Zone1 (Z1) Zone2 (Z2) Zone3 (Z3)

3

3.2.2. 双螺杆挤压机 : a. ZSK-30 (16L/D)

b. MP30PC

c. ZSK-25 (20L/D, MEGA Compounder, 最近供货的挤压机 – 委托 Krrup Werner Pfleiderer进行制造实验)

Zone2 (Z2)

Zone1 (Z1)

Zone1 (Z1) Zone3 (Z3)

Zone2 (Z2)

Zone1 (Z1)

Zone2 (Z2)

Zone3 (Z3)

Zone4 (Z4)

Zone5 (Z5)

Zone3 (Z3)

Zone4 (Z4)

安装 Undercut Profile Screw

4

3.3. 挤压机制造条件

3.3.1. PX4324 制造条件变化 Set Temp. / Actual Temp. (oC) Screw Sample

No. Type 挤压机 WK Z1 Z2 Z3 Z4 Z5 rpm Torque(A or %) Feeder

1 40 / 43 40 / 91 100 / 93 180 5.6A 200/min 2 40 / 42 40 / 88 100 / 99 250 4.7A 350/min 3 40 / 39 40 / 101 100 / 117 250 6.6A 450/min 4

PLK-461)

(DG Screw) 40 / 62 40 / 106 100 / 119 250 7.8A 550/min

5 30 / 39 30 / 114 100 / 118 250 6.6A 350/min 6 30 / 50 30 / 117 100 / 120 250 7.2A 450/min 7

PLK-461)

(DV Screw) 30 / 56 30 / 119 100 / 123 250 7.8A 550/min

8 ZSK-302) 100 / 99 100 / 99 100 / 102 100 / 102 300 9 MP30PC3) 30 / 30 97 / 96 98 / 97 450 50/min

10 20 / 20 40 / 39 100 / 103 100 / 102 100 / 102 300 42% 30kg/h 11 20 / 20 40 / 39 100 / 103 100 / 101 100 / 102 600 36% 40kg/h 12 20 / 20 40 / 40 100 / 104 100 / 103 100 / 103 600 44% 60kg/h 13 20 / 23 40 / 41 100 / 103 100 / 100 100 / 102 900 35% 60kg/h 14 20 / 21 40 / 40 100 / 103 100 / 102 100 / 103 900 42% 80kg/h 15 20 / 23 40 / 40 100 / 102 100 / 102 100 / 99 1200 34% 80kg/h 16

PX

4324

ZSK-254)

20 / 21 40 / 40 100 / 103 100 / 100 100 / 103 1200 40% 100kg/h 1)中研粉末涂料室的材料 2), 3)粉末研究部的材料, 4)委托KWP

a. 虽然 Buss Process Engineer 提出的 PX4324 制造条件与下表相同，挤压机的加热和冷却单位运转不稳定，如果没有更换 Screw Part的零件，这个条件下无法进行实验。

Set Temp. (oC) Barrel L/D Screw Type WK Z1 Z2 11 (KCC=> 7L/D) D Screw <50 <50 <60

b. Buss 挤压机生产 PX4324 时，在相同条件下，或者增加喂料的 rpm，或者把挤压机 DG 螺杆更换为 DV 螺杆，就会出现高温 (上升 10~20oC)的情况。

c. ZSK-30和 MP30PC的制造实验是粉末研究部实施的，制造条件和平时的条件相同。 d. PX4324委托给 KWP，使用现在正在开发销售的挤压机(ZSK-25)，在不同条件下制造实验。 e. KWP在进行 ZSK-25 制造实验时，增加 Screw rpm 和 Feeding 的量的时候，制造温度并没有上升，这和 Buss 挤压机制造时候的

5

想象不一致。 3.3.2. EX4411 制造条件变化

Set Temp. / Actual Temp. (oC) Screw Sample No. Type 挤压机 WK Z1 Z2 rpm Torque(A or %)

Feeder

F1 20 / 70 30 / 51 30 / 81 125 7.8A 250/min F2

EX4411 PLK-46 (DG Screw) 20 / 66 30 / 50 30 / 82 180 5.6A 300/min

a. Fast Curable Type的 EX4411难以由 Buss挤压机的 DV Screw中加工制造(预计在分散的时候生成胶状颗粒)，所以在 DG Screw中制造，在较低的温度条件下(Cold Operation Condition)进行。这个条件下的制造温度是根据摩擦热决定的。

b. 迄今为止快速固化式（Fast Curable Type）被认为难以在双螺杆挤压机中制造，为了解决这个问题，委托 KWP 进行制造实验，但是，因为 KWP的内部原因没有如期进行，只是向 KWP咨询了制造条件，在得到回信后将另行报告。

3.4. 硬化条件 Sample Type Curing Condition

PX4324 180oC x 15min EX4411 150oC x 15min

3.5. 性质测量方法

Item Method Remark Gelation Time Hot Plate, 180oC (PX4324)

150oC (EX4411)

Appearance Visual Gloss Glossmeter, 60o Color Datacolor CS-5

Impact Resistance DuPont Impact Tester, φ1/2” Thermal Properties DSC Tg, 熔点测量

6

3.6. 硬化过程中粘弹性（viscoelasticity）的特点变化分析(RPT-3000)

硬化中的粘弹性特点是使用 RPT-3000，在动态条件(10oC/min)下测量的，分析方法如下：

3.6.1. 上图是用 RPT-3000测量的粘弹性变化的典型例子，本实验也得到与此相似的结果。 3.6.2. 化学反应、物理的结合(Chain Entanglement)越增加交联密度（Crosslinking Density）也增加，如果挤压机内分散中的化学的反应发生

了反应，就可以假定测量 RPT-3000时，交联密度不大。但是如果 RPT-3000的交联密度不仅是化学的结合，如果还有物理的结合，就需要考虑到这个因素。

3.6.3. 虽然衰减率（Damping Ratio）得到的斜率可以由粘度的增加(Viscosity Increment)来说明，但是对此的理论根据还需要深入研究。但是本研究的结果是基于斜率的倾向与粘度增加倾向相似的假定得出的。

3.6.4. 衰减率（Damping Ratio）中得到两个峰值，仪器制造商的解释是树脂的熔点，但是这个组合是只适用了一种树脂(CC7630)。硬化剂 PCA-501 是 3%，实验中得到的熔点大约是 120o，与 74oC、102oC 有差异。所以，另外的推论是低温峰值是树脂的 Tg，高温的峰值是树脂的熔点。但是现在没有支持这个推论的数据。一般来说，通过 DSC得到的 Tg，熔点与 RPT-3000有很大的差异。

3.6.5. 分析 RPT-3000 的数据时还可以设定另外一个重要的假定，如果挤压机内不发生化学反应而可以均匀分散，RPT-3000 测量时候出现的

7

Phase变化点(1’st/2nd Change point, Crosslinking Starting Point等)可能出现的相对较快。即分散过程中如果化学反应使链长增加，分子的活性降低，硬化反应(或者硬化特点变化)可能推迟。

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4. 结果

4.1. PCA-501 based Powder Coatings (PX4324)的一般性质比较 Gloss Color DSC*

Sample No. 挤压机 Surface 60o L a b 1’st Tg,

oC Δ Hmelt, J/g (Tmelt, oC)

Impact Resistance Gel Time (sec)

1 Hazy 71 85.35 -20.03 0.94 58 2.89 (123 oC) Poor 202

2 Hazy 82 85.60 -20.21 0.91 58 1.80 (127 oC) 500g/30cm 195

3 Good 92 86.02 -19.94 0.91 58 - 1kg/30cm 185 4

PLK-46 DG Screw

Good 93 86.07 -20.07 0.93 56 - 1kg/50cm 196 5 Good 92 85.78 -20.46 0.76 56 - 1kg/30cm 180 6 Good 92 85.95 -20.19 0.87 57 - 1kg/50cm 187 7

PLK-46 DV Screw

Good 92 86.10 -19.93 0.93 57 - 1kg/50cm 203 8 ZSK-30 Good 86 86.09 -19.64 0.87 55 - 1kg/50cm 184 9 MP30PC Good 93 86.03 -19.71 0.93 51 - 1kg/30cm 208

10 Good 93 86.23 -19.85 0.91 53 - 1kg/50cm 198 11 Good 93 86.22 -19.90 0.84 54 - 1kg/50cm 195 12 Good 93 86.35 -19.71 0.95 54 - 1kg/50cm 184 13 Good 93 86.21 -19.93 0.84 54 - 1kg/50cm 181 14 Good 93 86.27 -19.84 0.88 55 - 1kg/50cm 194 15 Good 93 86.16 -20.00 0.81 54 - 1kg/50cm 188 16

ZSK-25 (MEGA)

Good 93 86.35 -19.62 0.89 54 - 1kg/50cm 184 *1’st Tg – before cure

4.1.1. 单螺杆挤压机 (PLK-46)的分散性和 Process Window a. 镀膜模糊的情况下，测量 DSC 的时候，得到 PCA-501 的熔点峰值。与 Pure PCA-501 的Δ Hmelt比较的时候样品 1 大约 71%，样品 2 大约 42%在分散过程中不熔化。即分散时 PCA-501 不完全熔化，分散也不均一，所以镀膜后出现模糊现象。有必要对大量制造的时候出现的模糊现象进行比较。

b. 把样品 1,2,3,4和 5,6,7进行比较时，发现制造温度即使很高对胶质形成的时间也没有大的影响。 c. 本实验无法用肉眼或者 Color Computer区分实验品之间颜色的差异。 d. 相同的螺杆、相同的 Screw rpm条件下，安培数在 7.2以上(参考前面记述的制造条件)的时候，冲击阻力（Impact Resistance）的

9

数据最好，即相同 Screw rpm，从喂料器获得的投入量越大，螺杆的负荷越高，对提高性质越有利。 e. 使用 DG螺杆时，根据温度和 rpm设定条件，外观和冲击的变化很大，但是使用 DV螺杆时，制造条件引起的性质的差别比较小。即使用 DV螺杆时，胶质时间不发生变化，分散性得到，显示了相对宽的 Process Window。

4.1.2. 双螺杆挤压机 (ZSK-30, MP30PC, ZSK-25)分散性和 Process Window a. 用 MP30PC制造时的冲击强度比 ZSK-30略高，但是无法假定在 MP30PC的最好条件下制造，这一点需要以后继续研究。 b. 在 ZSK-25(MEGA Type)上制造时，Screw rpm变为 300 ~1200，喂料速度变为 30~100kg/h，整体上性质不发生变化，情况良好，数据稳定。即 Process Window非常宽。

c. 比较 ZSK-30和 ZSK-25(MEGA)制造的粉末，除了光泽度以外，性质没有大的差别。 4.1.3. 单螺杆挤压机和双螺杆挤压机的比较

a. 观察用 DSC 测量的粉末的 Tg，用双螺杆挤压机制造的粉末的 Tg 整体上较低，可能是因为制造的时候预混合粉末（Pre-mixed Powder）在挤压机内停留的时间 (Residence Time & Distribution)比单螺杆挤压机短引起的，即随着单螺杆挤压机喂料的量增加，发生摩擦热使温度上升，停留的时间也相对长，所以在分散的时间里略微发生化学反应，使粉末的 Tg上升。

b. 制造条件变化时，双螺杆挤压机加工的产品性质变化较小，而单螺杆挤压机加工的产品的性质变化很大，根据这个实验结果，可以说双螺杆挤压机具有较宽的 Process Window。

c. 实验结果没有显示各种挤压机类型对色泽的影响。

10

4.2. PCA-501粉末镀膜 (PX4324)硬化时的粘弹性的特点比较 Damping Ratio Frequency

Sample No.

挤压机 Type 熔点

(oC)

1’st ChangePoint (min)

Viscosity Increment

Slope

2’nd ChangePoint (min)

Crosslinking Starting Point

(min)

CrosslinkingSlope

Crosslinking Balanced Point

(min)

Crosslinking Density

Tg (after Cure)

(oC)

1 101.9 17.6 0.157 19.5 17.88 -0.046 21.27 0.157 84.5 2 99.5 17.6 0.103 20.1 18.15 -0.042 21.85 0.157 85.6 3 104.0 17.2 0.193 19.0 17.75 -0.065 20.80 0.196 85.6 4

PLK-46 DG Screw

97.3 17.9 0.095 20.3 18.42 -0.038 22.17 0.142 84.5 AVG 100.6±2.0 17.6±0.2 0.137±0.040 19.7±0.5 18.05±0.26 -0.048±0.001 21.52±0.53 0.163±0.020 85.1±0.6

5 100.9 17.4 0.127 19.7 17.91 -0.055 21.15 0.179 88.0 6 102.1 17.2 0.156 19.3 17.69 -0.064 20.69 0.193 84.5 7

PLK-46 DV Screw

102.1 17.6 0.155 19.4 18.44 -0.062 21.49 0.190 83.5 AVG 101.7±0.6 17.2±0.2 0.146±0.013 19.5±0.2 18.01±0.31 -0.060±0.004 21.11±0.33 0.187±0.006 85.3±1.9

8 ZSK-30 104.6 17.1 0.148 19.3 17.63 -0.067 20.58 0.197 85.9 9 MP30PC 102.1 17.4 0.196 19.0 17.89 -0.065 20.78 0.190 85.9

10 102.1 17.1 0.173 18.9 17.82 -0.063 20.84 0.190 86.8 11 100.8 17.9 0.132 19.9 18.43 -0.046 22.16 0.171 84.5 12 100.8 17.0 0.207 18.4 17.49 -0.066 20.43 0.193 85.7 13 104.3 17.9 0.120 19.8 18.49 -0.048 21.94 0.167 85.6 14 102.1 17.1 0.189 18.8 17.58 -0.067 20.41 0.189 85.6 15 103.0 17.6 0.142 19.4 18.16 -0.052 21.71 0.186 84.5 16

ZSK-25 (MEGA)

102.1 17.0 0.170 18.5 17.64 -0.064 20.52 0.186 84.5 AVG 102.2±1.1 17.4±0.4 0.162±0.029 19.1±0.6 17.94±0.38 -0.058±0.008 21.14±0.71 0.183±0.009 85.3±0.8

4.2.1. 单螺杆挤压机(PLK-46)的分散性和 Process Window

a. 从上述数据可以看到，数据上的区别虽然很小，但是可以发现有意思的现象。即使用 DV螺杆制造的粉末硬化时，DG螺杆制造的粉末粘弹性的特点进行比较，

← Damping Ratio, Frequency中变化的点 (1’st/2’nd Change Point, Crosslinking Starting Point)迅速出现。 ↑ Slope的变化大。 → Crosslinking Density密度大。

b. 这个结果是本报告前半部分记述的“如果不发生挤压机内分散均匀、化学反应引起分子链加长、分子的流动性降低的话，测量 RPT-3000的时候出现的 Phase变化点(1’st/2nd Change point, Crosslinking Starting Point等)可能相对快速出现”，“如果挤压机内分散的过程中不发生化学的反应，测量 RPT-3000时，可以预测 Crosslinking Density出现较大的差异”，与假设的情况比较一致。

11

c. 硬化后薄膜的 Tg没有随着螺杆类型的变化而发生差异。 4.2.2. 双螺杆挤压机 (ZSK-30, MP30PC, ZSK-25)分散性和 Process Window

a. 双螺杆挤压机的种类不同并没有带来明显的区别，这是因为 ZSK-30和 MP30PC的实验数据不够充分引起的。所以以后只涉及 ZSK-25的数据分析。

b. 如果观察相同的 Screw rpm、只增加喂料时 (对 Sample 11→12, 13→14, 15→16的数据进行比较时)显示的现象， ← Damping Ratio, Frequency中的变化的点(1’st/2’nd Change Point, Crosslinking Starting Point)迅速出现。 ↑ Slope的变化大。 → Crosslinking Density大。 c. 在相同喂料量、提高 Screw rpm的情况下 (比较 Sample 12→13, 14→15 的数据时)，显示与“b”的结果相反的现象。 d. 如果前面的假设正确，如果以“b”、“c”的结果固定 Screw rpm，那么增加喂料量，将提高分散性。 e. 随着分散条件的变化，硬化后的 Film Tg并未显示不同。

4.2.3. 单螺杆挤压机和双螺杆挤压机的比较 a. PLK-46(DV Screw)和 ZSK-25 制造的粉末的粘弹性的特点数据除了 Viscosity Increment Slope，得到的其他数据相似。特别是如果观察 Sample 6, 7的结果，用 PLK-46(DV Screw)制造时，增加喂料量时，如果螺杆的扭矩增加(7.0A以上)，和双螺杆挤压机的分散性将接近相似。

b. 但是双螺杆挤压机出现相对宽的 Process Window，这异味着用双螺杆挤压机制造时粉末的分散性对制造条件不敏感，可以实现稳定的生产。

12

4.3. Fast-curable Powder Coatings (EX4411) 一般性质比较 Gloss Color DSC* Sample

No. Surface 60o L A b 1’st Tg, oC

Δ HRXN, J/g (TRXN, oC)

2’nd Tg, oC

Impact Resistance Gel Time (sec)

F1 Texture 11 62.89 -11.96 20.19 70 48.4 (134 oC) 112 1kg/30cm 22

F2 Texture 8 61.61 -11.03 18.22 70 48.7 (134 oC) 110 1kg/30cm 23

*1’st Tg-before cure, 2’nd Tg-after cure

4.3.1. 根据 Buss Engineer 认为采用 DV 螺杆式难以制造的意见（如前面实验结果中看到的，DV 螺杆制造过程中温度上升幅度大，极有可能发生 Fast-curable Powde的硬化反应），所以采用 DG螺杆制造 Fast-curable Powder Coatings。

4.3.2. 上表中记述的胶化时间是在 150oC测量的结果，180oC测量时时间是 10秒以下，无法得到精确数据。迄今为止粉末研究部和涂料组一直认为双螺杆挤压机无法制造这个产品，所以只在单螺杆挤压机(DG Screw)中进行实验。

4.3.3. 在一般的制造条件下，制造的极限值是 2~3kg，在本实验条件下制造了 10kg以上，Gelation等过程没有出现异常。 4.3.4. 在本实验条件下制造的粉末在一般性质方面未表现差异。 4.3.5. Buss Process Engineer 认为，加热/冷却系统正常运转，如果使用更大的产品出口 Die Hole Size(本实验采用 16mm)的时候，Fast-

curable Powder Coating制造时未出现问题。对于这个事项，应该在量产试验的时候参考。

13

4.4. Fast-curable Powder Coatings (EX4411) 粘弹性特点比较 Damping Ratio Frequency

Sample No. 熔点

(oC)

1’st Change Point (min)

Viscosity Increment

Slope

2’nd ChangePoint (min)

Crosslinking Starting Point

(min)

Crosslinking Slope

Crosslinking Balanced Point

(min)

Crosslinking Density

Tg (after Cure)

(oC)

F1 96.1 8.2 0.333 9.1 10.26 -0.043 13.98 0.160 123.2 F2 97.5 8.4 0.357 9.4 10.26 -0.038 14.61 0.167 125.7

4.4.1. 测量 RPT-3000 时，本产品的特点方面，熔化和化学反应几乎同时发生，难以精确测量 Viscosity Increment Slope/Crosslinking

Slope。 4.4.2. 只参考上述数据观察制造条件变化引起的粘弹性特点变化尚不充分。 4.4.3. 粉末研究部使用的 Buss 挤压机的加热和冷却系统状态不良，无法在各种条件下进行实验，观察到的各种分散程度引起的一般性质和粘

弹性变化的数据不充分。

14

5. 结论与讨论

5.1. 往复单螺杆挤压机和双螺杆挤压机的比较挤压机的类型往复单螺杆挤压机

PLK-46 双螺杆挤压机

ZSK-25(MEGA) Screw DG Type DV Type Undercut Profile Screw 包含分散性不良良好良好 Process Window 比较窄窄宽

生产效率 ? ? ? 适合制造 Fast-curable Powder Coating 难以制造 Fast-

curable Powder Coating 未确认能否制造 Fast-curable Powder Coating

Remark

根据粉末镀膜类型改变螺杆类型最合适，Buss Process Engineer 推荐对各种类的粉末的分散最有利、Process Window最宽的 D螺杆。

5.1.1. 试验测试 Buss 单螺杆挤压机的性能的时候，没有在 Buss 上提高性能、没有在最近销售的 PCS-30 上实验、备件不足，无法认为在良

好状态下进行了实验。特别推荐在 Buss中，Barrel length比一般(7L/D)长（11L/D）。所以，对于上述结果应该考录这个情况。 5.1.2. 在 ZSK-25安装 Undercut Profile Screw来加工微粉的情况下进行了制造实验，最近趋势是提高这种喂料能力的螺杆。

5.2. 意见

5.2.1. 现在的 PLK-100的螺杆由 DG类型更换为 D或者 DV型，提高分散性，需要对加宽 Process Window的方案进行积极的研究。 5.2.2. 用 Buss单螺杆挤压机生产 Rebar用的 Fast-curable Powder Coating时，需要研究对加大出口 Die Hole Size抑制 Gelation等问题、

提高生产效率的方案。 5.2.3. 现在炭黑等微粉含量多的产品的分散时，向挤压机内投入的状况不良，所以少量掺加有机溶剂(Xylene)，但是这个防范需要使用另外的

溶剂，降低产品的收率，残留的溶剂还可能引起镀膜的不良，高温分散时溶剂发挥、引起环境问题，还有可能对操作人员造成危害。所

以需要研究使用各挤压机企业推荐的微粉用螺杆、不需要掺加有机溶剂、使微粉的投入更容易的方案。 5.2.4. 最终，为了提高质量、保证生产的稳定性，需要积极改善改良生产设备，需要购置新开发的优秀挤压机。

TECHNICAL BRIEF

THE POWDER COATING INSTITUTE

2121 EISENHOWER AVENUE, SUITE 401, ALEXANDRIA, VIRGINIA 22314

HEALTH & SAFETY

INFORMATION

ON

β-HYDROXYALKYLAMIDE

CROSSLINKER

The material provided in PCI Technical Briefs is for general informational purposes

only. Always consult an expert in powder coating before attempting actual applications.

HEALTH AND SAFETY INFORMATION ON

β-HYDROXYALKYLAMIDE CROSSLINKER

TABLE OF CONTENTS

Page

A. SUMMARY

B. INTRODUCTION

C. CHEMISTRY

D. TOXICOLOGY OF β-HYDROXYALKYLAMIDE

1. Health Effects Testing

2. Environmental Effects Testing

E. EXPOSURE, AND INDUSTRIAL SAFETY CONSIDERATIONS

1. General Considerations

2. Exposure Considerations

3. Risk Considerations

4. Industrial Safety

5. Workplace Exposure Recommendations

6. Disposal

F. REFERENCES

G. GLOSSARY

H. APPENDIX

1. Worldwide Regulatory Status

1

2

2

4

4

5

6

6

6

7

7

8

8

9

12

13

A. SUMMARY

β-Hydroxyalkylamide (HAA) crosslinker* is a curing agent for thermoset

powder coating applications. β-Hydroxyalkylamide is used in formulated

products in which it is bound inescapably within a polymer matrix. This

paper is structured to provide information about the inherent safety of

HAA on the basis of chemistry, toxicity, and exposure considerations

known to date. The paper outlines general recommendations for good

industrial hygiene parctices to minimize risks of exposure.

The health and safety data generated on this chemical suggest that HAA

poses a very low risk for adverse health effects in workers, formulators,

or the public. β-Hydroxyalkylamide’s physical/chemical properties and

subchronic (repeated exposures) toxicity studies, or in

genotoxicity/mutagenicity studies all suggest that adverse effects should

not occur if exposure to HAA dust is controlled to levels representing

the industry maximum of 10 mg/m3. The chemical is not expected to

pose any significant occupational hazard as a result of use, adverse work

conditions, limited or confined spaces, or proximity to other chemicals. It

is not expected to react with water or other chemicals normally

encountered in the workplace. As with any organic material, contact with

strong oxidizing agents should be avoided. The environmental risks

associated with HAA are considered to be extremely low because it will

not be released to the environment except in accidental spills (low

probability), but even if it were released, it has an extremely low toxicity

to terrestrial and aquatic organisms.

In summary, on the basis of its toxicology and environmental profile,

HAA crosslinker can be used safely and with very low associated risk for

adverse effects on health or the environment when good industrial

hygiene practices are followed.

*HAA reffered to in this paper is Bis(N,N’-dihydroxyethyl)adipamide.

B. INTRODUCTION

The unique ability of HAA’s to crosslink with carboxylic acid functional

polymers was first described in the late 1970’s (Lomax and Swift, 1978).

Though HAA’s were shown early on to have utility as crosslinkers in

exterior grade powder coatings applications, it was not until 1990 that

Bis(N,N’-dihydroxyethyl)adipamide, the first HAA specifically developed

for the powder coating industry, was introduced by the Rohm and Haas

Company.

C. CHEMISTRY

β-Hydroxyalkylamide is a water soluble, crystalline solid (M.P.= 120 to

124℃) which consists predominantly of Bis(N,N’-

dihydroxyethyl)adipamide ( >90%), the structure shown in Figure 1.

< Figure 1. Structure of Bis(N,N’-dihydroxyethyl)adipamide >

Small amounts of higher molecular weight condensation products, such

as the ester-dimer shown in figure 2, are also present.

< Figure 2. Structure of Ester-Dimer >

The ester-dimer, as well as other higher order condensation products

found in HAA are all active crosslinkers.

β-Hydroxyalkylamide reacts with carboxylic acid functional polyester

resins to form a crosslink network through a condensation esterification

reaction. Consequently, for each new ester bond formed, a molecule of

water is released. Compared to conventional alcohols or polyols,

HAA curing agents react

readily with acid functional

polymers

Curing process occurs via a

condensation reaction.

CH2 CH2 CH2 CH2 CC NN

O CH2CH2OH

CH2CH2OH

OHOH2CH2C

HOH2CH2C

CH2 CH2 CH2 CH2 CC NN

O CH2CH2OH

CH2CH2O

OHOH2CH2C

HOH2CH2C CH2 CH2 CH2 CH2 C N

O CH2CH2OH

CH2CH2OH

C

O

HAA’s are considerably more reactive. This is believed to be due to the

ability of the HAA to form a highly reactive oxazolinium intermediate at

temperatures above about 130℃ (Wicks et al., 1985). Once formed, this

intermediate readily reacts with the available carboxylic acid groups to

form a new ester bond.

Table 1. Physio-Chemical Properties

PRODUCT DATA

PRODUCT: PCA-501

PRODUCT DATA

Appearance white crystalline solid

Bulk-Density [g/cm3] approx. 0.7

Colour, Gardner ISO 4630 max. 1.0

Melting point DIN 53181 [℃] 120-124

Water content DIN 51777 [%] max. 1.0

Hydroxy value [mgKOH/g] 600-725

D. TOXICOLOGY OF β-HYDROXYALKYLAMIDE

1. HEALTH EFFECTS TESTING

The toxicology of HAA has been investigated extensively. β-

Hydroxyalkylamide has proven to be generally without adverse effect in

a wide variety of studies. In single-dose studies by the oral and dermal

routes, HAA is considered to be “practically non-toxic”, based on

lethality. The median lethal dose (LD50) was greater than 5.0 g/kg both in

rats (oral) and rabbits (dermal) (Lampe and Baldwin, 1988). Irritation

studies in rabbits showed β-Hydroxyalkylamide was essentially non-

irritating to skin (4-hr Mean Irritation Score=0.0) and inconsequentially

irritating to the eyes (Lampe and Baldwin, 1988). In a guinea pig skin

sensitization test,HAA produced no evidence of allergic contact

dermatitis or sensitization to skin (Parcell and Baldrick, 1990).

In three Ames Bacterial mutagenicity studies, HAA was found not to be

mutagenic and showed no response (increase in reversion frequency) in

any of 5 strains of Salmonella typhimurium (Kirby, 1988; Jones et al.,

1990) nor in E. coli. (Jones and Gant, 1994). Similarly, it was not

mutagenic in mammalian cells. In Chinese hamster ovary (CHO) cells,

HAA did not produce forward mutations at the HGPRT locus (Adams and

Kirkpatrick, 1993). In two additional in-vitro cytogenetics studies in

cultured CHO cells, HAA did not induce chromosomal aberrations or alter

mitotic index (Brooker, et al., 1990; Jones et al., 1993). Thus HAA

showed no evidence or potential for mutagenic or clastogenic activity.

In a 28-day repeat oral gavage study in rats at concentrations ranging

from 10 to 1000 hg/kg/day (the ‘limit’ or maximum allowable dose), no

treatment-related systemic toxicity was observed. Increased liver and

kidney weights were found in male and female rats of the 1000

mg/kg/day group, but there were no corresponding histopathologic

changes or untoward systemic effects attributable to HAA in any of the

animals. Thus 1000 mg/kg/day was considered to be the No Observed

Adverse Effect Level after repeated administration (Edwards et al.,

1990).

HAA is practically non-toxic

via oral or dermal

exposures, is non-

sensitizing & non irritating

to skin & eyes.

HAA is non-mutagenic.

HAA causes no systemic

toxicity with repeated oral

exposures.

In a one-generation reproduction study in rats (Shuey et al., 1994), a no

observed effect level (NOEL) for general toxicity in parental animals of

4500 ppm was determined. At 20,000 ppm, indications of toxicity were

limited to soft and/or irregular feces in both sexes. Due to their delayed

onset, the toxicological significance and relationship to treatment of

these signs were considered equivocal.

2. ENVIRONMENTAL EFFECTS TESTING

In environmental fate and ecotoxicity studies, HAA was practically non-

toxic to daphnia, trout, and algae. In daphnia, the 48-hr median effective

concentration (EC50) for immobilization was > 1000 mg/L, the ‘limit’ test

concentration (Douglas et al., 1990). In trout, under semi-static test

conditions, the 96-hr median lethal concentration (LC50) was > 1000

mg/L, also the ‘limit’ concentration (Douglas et al., 1990). In algae, the 72

hr. median effective concentration EC50 was > 97 mg/L (Douglas et al.,

1993). β-Hydroxyalkylamide was practically non-toxic to earthworms

over a 14 day exposure to the limit concentration of 1000 ppm. (LC50 >

1000 ppm) (Caley et al., 1992).

β-Hydroxyalkylamide was stable to hydrolysis over 5 days, showing less

than 10% hydrolysis at pH 4 (t1/2 > 1 yr); 10% hydrolysis at pH 7 (t1/2 = 1

yr); and 20% hydrolysis at pH 9 (t1/2 < 1 yr) (Hossack et al., 1990). At

elevated temperatures of 60 and 70℃ at pH 9, rate constants for

hydrolysis were calculated and extrapolated to calculate a half-life of

113 days for HAA at pH 9 and 25℃ (Macdonald et al., 1991). In a test

using bacteria in activated sludge, HAA was not readily biodegraded

(~4-5% degraded) within 28 days (Oyama, 1990). Follow-up studies

showed HAA did not inhibit respiration of activated sludge; the 3-hr

respiration inhibition EC50 was > 1000 mg/L (Douglas et al., 1993).

Although HAA does not readily degrade abiotically or biotically, it has

little or no toxicity in any aquatic (or mammalian) species tested.

In a bioconcentration study in carp (Nishikawa, 1998) HAA was tested

for its bioaccumulation potential. The resulting bioconcentration factors

obtained were far below 15 at the high exposure level of 10 mg/L and far

below 100 at the low exposure level of 1 mg/L HAA was not

bioaccumulative under the conditions of this study.

Thus, all health effects (toxicity) and ecotoxicity studies suggest that

HAA is virtually without remarkable adverse effect to human health or

the environment even at doses representing the highest allowable

concentrations for these tests.

HAA shows no

reproductive toxicity

up to 20,000 ppm

HAA is proctically non-

toxic to aquatic life.

HAA is practically non-toxic

to terrestrial life.

HAA is not

bioaccumulative.

Based on animal testing,

HAA would not be

anticipated to have adverse

effect on humans

E. EXPOSURE AND INDUSTRIAL SAFETY CONSIDERATIONS

1. GENERAL CONSIDERATIONS

β-Hydroxyalkylamide crosslinker is a white crystalline solid with an

amine odor. Ii has a molecular weight of 320; vapor pressure of 0.003

mm Hg; Log Pow = -2.50 (21℃); water solubility at 608.3 g/l (at 20℃);

pH 9-10; melting point of 120-124℃ flash point of 104 ℃; and,

decomposition temperature of 250℃. As such, HAA is non-volatile, non-

flammable, non-explosive, with high water solubility but no potential for

bioaccumulation.

β-Hydroxyalkylamide is used to crosslink electrostatic spray-applied,

thermoset powder coatings for metals. After curing, the thermoset

powder coatings are predominantly solid film coatings of water insoluble,

high molecular weight polyester resins with highly stabilized pigments

and inert extender pigments. It is believed that the solid polymer matrix

incorporates or encapsulates HAA, the crosslinking agent. Because low

levels (2 to 3%, based on total powder coating) of HAA are used,

incorporation or final encapsulation is expected to reduce any residual

level availability from the solid polymer matrix. Thus, the use of HAA in

coatings of consumer goods is expected to have virtually no impact on

public health. Since this material is used for industrial application alone,

there is virtually no opportunity for exposures from domestic use.

Industrial accident provides the only opportunity for public exposure ,

and that probability is slight. In the industrial setting, there are basically

four unit operations which provide opportunity for industrial exposure to

the total powder coating containing HAA; blending, extrusion, grinding,

and spraying.

2. EXPOSURE CONSIDERATIONS

The physical properties of HAA do not support inhalation as a relevant

route of exposure. As a solid grade material with a relatively low vapor

pressure, large particle size, and high melting point, HAA is not expected

to be present in significant levels in the workplace as a vapor under

expected use conditions. The chemical could be encountered in the

workplace as a dust during manufacture or formulation. Particle size

distribution studies on HAA indicate that material will not readily

aerosolize under normal conditions due to its large particle size (75-

>200㎛) and its tendency to aggregate once it becomes airborne. There

is no evidence of a significant respirable particle fraction (<15㎛) with

this material.

HAA has no labeling

triggers.

There is little chance of

public exposure to HAA.

HAA is virtually non-

respirable.

A comprehensive study of potential worker inhalation exposure to HAA

during various handling operations revealed insignificant exposures to

the material, even under conditions of no local exhaust ventilation. At

worst, airborne HAA behaves no worse than a so-called nuisance dust.

Air monitoring for HAA using both personal and area air samplers

confirmed airborne levels of the material which were many times less

than the established HAA Workplace Exposure Limit (WEL) and the

ACGIH Threshold Limit Value (TLV) for total dust (10mg/m3). Under

conditions where local exhaust ventilation is present, levels of HAA in

the breathing zone of workers were below the analytical defection limit.

Inhalation exposure to HAA during the baking process is unlikely. Proper

exhausting of the oven will prevent any appreciable amount of material in

the breathing zone of workers.

Even under extreme worst-case conditions, levels of HAA still generally

remain well below the WEL for the material due to its large particle size

and its tendency to clump and aggregate once airborne. Due to the low

potential for an appreciable amount of HAA to become airborne, the

associated dermal exposure to settled material on work surfaces is also

minimal. The amount of settled HAA on work surfaces monitored during

post-extrusion operations revealed minimal amounts of the material for

dermal contact.

3. RISK CONSIDERATIONS

Any potential inhalation exposure to decomposition products of HAA can

be avoided through the use of proper and adequate exhaust ventilation in

the workplace. Exhaust rates in any oven work environment must be

sufficient to prevent the build-up of combustion products or smoke in the

workplace. The breathing of any smoke in the workplace should be

avoided.

4. INDUSTRIAL SAFETY

Supplied exhaust ventilation in the workplace must be sufficient to

prevent the build-up of any hazardous airborne materials and to keep

airborne dust levels below the 10 mg/m3 maximum exposure limit.

Although HAA has a low propensity to become airborne, proper airflow

must be maintained in powder coating spray booths to contain the

powder and to prevent exposure potential to combustion products which

may be formed if the powders are drawn into the oven combustion areas.

Combustion ovens should not be vented into the workplace, and should

be properly vented to the outside. Air from the workplace should always

flow into the oven openings. The appearance of haze or smoke in the

At worst, HAA can be

handled as a nuisance dust.

Breathing of

combustion or de-

composition

products from HAA

should be avoided.

Maintain good

workplace exhaust/

ventilation.

workplace is an indication that the oven exhaust system is no properly

functioning. Any questions on the air quality of the workplace should be

referred to an industrial hygienist.

Although HAA has a low toxicity and low potential for dermal exposure,

powder coatings may be abrasive if left on the skin for long periods of

time or if they are rubbed into the skin. Exposed skin that has come in

contact with powder coatings should be flushed promptly with water and

washed with mild soap. Any skin irritation from the coatings may be

avoided through the use of proper industrial hygiene measures such as

the use of chemically resistant gloves.

5. WORKPLACE EXPOSURE RECOMMENDATIONS

In the industrial setting, the workplace exposure limit (WEL) for HAA has

been set at 10 mg/m3, consistent with nuisance dusts. The basis for this

is extrapolation from the no observed adverse effect level (NOAEL) of

1000 mg/kg/day in the 28-day subchronic oral study. This daily dose is

equivalent to an airborne concentration of approximately 7000 mg/m3 per

8 hr workday. Applying a safety factor of 1000 (an overly conservative

margin of safety relative to the NOAEL) would yield a WEL of 7 mg/m3,

based on total dust. In light of the virtual lack of toxicity seen with this

material and the overly conservative application of 1000 as safety

margin, and the very low propensity for HAA to be respired, the Health

Hazard Review Committee of Rohm and Haas Company rounded the

time-weighted average to 10 mg/m3 (consistent with nuisance dusts) on

October 25, 1991. A short-term exposure limit (STEL) value was not

considered necessary.

6. DISPOSAL

The powder coating material that is disposed typically consists of a solid,

water insoluble high molecular weight polyester resin and highly

stabilized prime pigments and inert extender pigments. The solid

polymer matrix encapsulates the crosslinking agent. Disposal is generally

to a secure landfill site at a facility that complies with local, state, and

federal regulations.

Wash skin exposed to

powder coating promptly

with water and mild soap.

Workplace exposure level to

HAA is the same as for

nuisance dust or 10 mg/m3.

Dispose of HAA containing

powder coating in

accordance with local, state

and federal regulations.

F. REFERENCES

HEALTH AND SAFETY INFORMATION ON β-HYDROXYALKYLAMIDE CROSSLINKER authored

by; James E. McLaughlin, Phd., Toxicology Department, October, 1994.

Mammalian Cell Mutation Assay, Huntingdon Research Centre, Ltd., September 1993. OECD

Guideline 476

British Industrial Biological Research Association (BIBRA), Toxicity Profile of Diethanolamine.

1988

Brooker, P.C., Paterson, K.M.A., King, J.D., Gray, V.M., Huntingdon Research Centre, Ltd., June

1990. OECD Guideline 473.

Caley, C.Y., B.E. Hall, B. Knight ; Determination of Acute Toxicity in Earthworms (14 Day, Limit

Test) Inveresk Research International, November, 1992. OECD Guideline 207.

Douglas, M.T., Stonehewer, R.O., Macdonald, I.A., Huntingdon Research Centre, Ltd., August 1990.

OECD Guideline 202, Part 1 and EEC Directive 67/548 Annex V C.2 as published in 84/449/EEC.

Douglas, M.T., Stonehewer, R.O., Macdonald, I.A., Huntingdon Research Centre Ltd., August 1990.

OECD Guideline 203 and EEC Directive 67/548 Annex V C.1 as published in 84/449/EEC.

Douglas, M.T. and D.R. Ffrench; Inhibitory Effect on the Respiration of Activated Sewage Sludge,

Huntingdon Research Centre, Ltd., January, 1993. OECD Guideline 209 and EEC Directive 67/548

Annex VIII Part C (87/302/EEC).

Douglas, M.T., D.R. Ffrench, I.A. Macdonald; Algal Growth Inhibition Huntingdon Research Centre,

Ltd., February, 1993. OECD Guideline 201 and EEC Directive 67/548 Annex VIII Part C.

Edwards, J.A., Parcell, B.I., Crook, D., Gibson, W.A., Read, R.M., Gopinath, C., Macdonald,I.,

Howes, D.A., Huntingdon Research Centre, Ltd., July 1990. OECD Guideline 407, EEC Directive

79/831/EEC.

Hossack, D.J.N., Macdonald, I.A., Flack, I., Huntingdon Research Centre, Ltd., April 1990. EEC

Directive 67/548, Annex V, Part C, Test C10 as published in 84/449/EEC.

F. REFERENCES (Continued)

Jones, E., Cook, P.G.S., Gant, R.A., Kitching, J.; Bacterial Mutation Assay, Huntingdon Research

Centre, Ltd., May 1990. OECD Guideline 471.

Jones, E. and R.A. Gant ; Bacterial Mutation Assay, Huntingdon Research Centre, Ltd., 1994. OECD

Guideline 471 and 472; MITI No. 1014.

Jones, E., M.A.K. Paterson, A. Howell, and D.H. Anderson ; Analysis of Metaphase Chromosomes

Obtained from CHO Cells Cultured In Vitro, Huntingdon Research Centre, Ltd., February, 1993.

OECD Guideline 473, EEC Directive 79/831/EEC.

Kirby, P.E., Sitek Research Laboratories, July 1988. OECD Guideline 475, US EPA 40 CFR Part

158. 135; Guideline 84-2.

Lampe, K.R., Baldwin, R.C. ; August 1988. OECD Guideline 404, US EPA 40 CFR Part 158;

Guideline 81-5.

Lampe, K.R., Baldwin, R.C. ; August 1988. OECD Guideline 410. US EPA 40 CFR Part 158;

Guideline 81-1.


Guideline 81-2.


Guideline 81-4.

Lomax, J. and Swift, G.,; J. Coatings Tech. 50:49 (1978); Swift, G. and H.J. Cenci. US Patent

4076917, Feb. 28, 1978; Cenci, H.J. and g. Swift US Patent 4101606, Jul 18, 1978.

Macdonald, I.A., Howes, D.A., Betteley, J., Howell, K., Huntingdon Research Centre Ltd., October

1991. EEC Directive 67/548, Annex V, Part C, Test C10 preliminary test as published in

84/449/EEC.

Nishikawa, Ayao, Mitsubishi Chemical Safety Institute Ltd., December 1998. OECD Guideline 305C.

Oyama, I., Kurume Research Laboratories, March 1990. OECD Guideline 301C.

Parcell, B.I., Baldrick, P., Huntingdon Research Centre, Ltd., August 1990. EEC Direct 84/449/EEC

(OJ No. L251, 19.9.84), Part B, Method B6 Acute toxicity (skin sensitization).

F. REFERENCES (Continued)

Shuey, D.L, Romanello, A.S., and Lomax, LG. ; One-Generation Study in Rats, December 1994.

OECD Guideline 415.

Wicks, Z.W. Jr., Applet, M.R., and Soleim, J.C., J. Coatings Tech., 57;51 (1985)

G. GLOSSARY

Acute tests

LD50

NOAEL

Carcinogen

Clastogen

Mutagenicity

In-Vivo

In-Vitro

Protocols

Sensitizer

Studies designed to test the effects of single exposures to a

chemical. Route of exposure may vary from oral gavage

(forced feeding via stomach tube), dermal (applied under a

patch to the skin), or inhalation (dusts, vapors, or aerosols of

a material introduced into a chamber).

The median lethal dose (e.g. mg/kg body weight), that is

required to produce lethality in 50% of the treated population

following a single exposure. Similarly, LC50 refers to the

median lethal concentration (e.g. mg/L) of a material as

measured in water or air.

No Observed Adverse Effect Level. That dose at which no

adverse effects to health, behavior, or organ systems

attributable to treatment, were noted to occur.

A material which has been demonstrated to cause cancer in

humans or laboratory animals.

A material that causes chromosomal breaks or damage.

The induction of changes or mutations in genetic material or

sequence as a consequence of exposure. Induction of

development of cancer. Mutagenicity studies may be done in

bacterial systems (Ames test) or in mammalian cells

(CHO/HGPRT assay).

Studies conducted in intact, living organisms or systems to

evaluate endpoints resulting from exposure to a substance.

Studies conducted ‘in testtube’ or in non-living systems.

Studies done on cultured cells growing in glass culture dishes

are considered in-vitro assays.

Methodology defined to conduct studies according to

applicable laboratory and/or governmental guidelines.

A chemical substance that induces, after the initial contact, a

hypersensitive allergic or exaggerated skin response upon

subsequent exposures, even at levels which ordinarily would

not be irritating

APPENDIX 1. WORLDWIDE REGULATORY STATUS (12/00)

COUNTRY

USA

Europe

Norway

Switzerland

Canada

Japan

Australia

New Zealand

Korea

China

Thailand

Latin America

INVENTORY STATUS

OK–No Federal, State or Local Restrictions of sales.

PMN Approved (Reached Level 2 Trigger, 1000 Metric Tons)

Commercial Sales permitted in all EEC states.

PMN not required, Commercial sales permitted.


Commercial sales permitted. A submission to Domestic

Substance Labeling has been completed.

MITI approval gained April 19, 1999.

PMN approved 12/91, Commercial sales permitted by EMS-

PRIMID.


OK–trade name certification has been granted.

OK–trade name certification has been granted.

OK–CAS-No. is listed in the chemical inventory.


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