DEN ATI No. 331 ‘DENKA CHLOROPRENE Technical Information pmemrmrrmcmeme nme menme rm nme me oy INTRODUCTION to DENKA GR ADHESIVE GRADES | mrom meen cme emrrae sme rm ene nme aw amre ara al QENKI KAGAKU KOGYOU KABUSHIKI KAISHA. | OMI PLANT POLYMER TECHNOLOGY INSTITUTE ELASTOMER RESEARCH DEPARTMENT Omi 2209, Itoigawa-shi Niigata Pref, 949-0393 JAPAN Tel: +81-25-562-6552 Fax: +81-25-562-6488INTRODUCTION TO DENKA CHLOROPRENE FOR ADHESIVE GRADES CONTENTS - 1, CHARACTERISTICS of DENKA CHLOROPRENE 2. SOLUTION VISCOSITY of DENKA CHLOROPRENE 3. BASIC PROPERTIES of GENERAL GRADES 4, BASIG PROPERTIES of A-30 5, BASIC PROPERTIES of A-400 6. BASIC PROPERTIES of A-91 7. BASIC PROPERTIES of DCR-11 8. BASIC PROPERTIES of A-90S and DCR-16 9. BASIC PROPERTIES of DGR-15L and H 10. BASIC PROPERTIES of DCR-25Table 1 CHARACTERISTICS of DENKA CR ‘Mooney Type & Grade Viscosity (MS2+2.5) Original Grade Low Viscosity t General purpose Extremely high viscosity Easy mastication, Fast cure Long tack time 2710~5000% Low solid content 48 + 4 High reactivity with isocyanate 80 uprer High thixotropio. High viscosity 2710~ 4000 Low solid content 4 Light color chip Clear color solution Note: % — 5%in toluene solution vis. (mPa-s) at 20°C ‘ee 10% in toluene solution vis. (mPa-s) at 20°C we Mooney vis. (ML 1+4) at 100°C [COMMENTS] *DENKA has been producing chloroprene rubber since 1962. 4DENKA Chloroprene adhesive grades, such as A-90, have been highly evaluated in the market. +#In this literature, the properties of both general and special grades of DENKA Chioroprene are introduced.DCR-30 M=120 | L4er20 7) | | . M-130L. / oy; saoamasttteney oe :DOR 151 Low vis. High s.c. DGR-25 | IDCR-15H) Good brushabilty, spray | ‘A-400 High vis. Low s.c. High strength at Initial & Heat Lov crystallization rate High crystallization rate Long tack time & good flexibility » ‘igh bonding strength Fig. 1 Systematic Chart of DENKA CR Adhesive Grade [COMMENTS] This chart shows the basic characteristics of each grade. -3-‘uonnjosip 2941p 404 xepul ue eq Uo e4naBy siy ‘SIA UORNJOS pue LORNJos aUANjo} UI U9]U0D pljos UBEMzEq diysuOAEIe4 ay} sMOYS Ydesd SIYJ s¢ [SLNAWWOO] YD WINIA #0 ALISODSIA NOLLITIOS Z 24 (% ) eu@N|o3 UL qUEQUOD pI|Og si oO s st ol $ ob 2 g (8-2qu) AYsoosIA UORN|OS 0000) 000001Table 1 CHARACTERISTICS of DENKA CR Grade A-30 | A-70 | A-90 | A-i00 | A-120 Crystallization rate Fast | Fast_| Fast | Fast | Fast Chip size Small_[/Smatt_[ Small_| Small_[ Small Mooney vis(MS2+2.5) [SPEC] 2043 | 4043 [ 4844 [ 5745 [ 6745 Solid content (8) 2 28 27 26 25 Initial strength (N/mm), aie | 024 | 026 08 0.42 Final strength (N/mm) 11.0 108 tos | 108 Strength at 60:C (N/mm) 05 17. 24 26 Tack retention time (hr) 18 18 16 18 Grade TA-85 Crystallization rate Fast, Chip size ‘Small Mooney vis(MS2#2.6) [SPEC] 445 Solid content () 28 Initial strength (N/mm) 0.26 Final strength (N/mm) 10.2 ‘Strength at 60°C (N/mm) 15, Tack retention time (hr) 18 Grade M-40 | M-100 |M-130L|M-130H[DCR-25 Crystallization rate Medium [ Medium | Medium | Medium | Medium Chip size Large | Large | Small | Small | Small Mooney vis(MS2+2.6) [SPEC] 48:5 |100+10[ — _ = Solution vis(mPa‘s, 10% Tol} — = __|1000-1500] 1510-2700]2710-5000} Solid content (#) at 26 25 23 21 Initial strength (N/mm) o22 | 029 | 0.60 067 | 075 Final strength (N/mm) 75, 78, 82 84 9.0 Strength at 60°C (N/mm) 09 24 28 32.0 32, Tack retention time (hr) 30 28 26 26 26 Cts] # Both A-type and TA-type have fast crystallization rate, which gives higher final bonding strength. & Either initial strength or high temperature strength does not depend on the type(A,TA,M) of CR, but depends on the molecular weight. The larger the molecular weight, the higher the initial strength and high temperature strength. # Usage of higher molecular weight grade achives better cost performance.Test method for Table 2 1. Viscosity of Raw Polymer 1) Mooney viscosity ML1+4 at 100°C after 10 pass by open roll, nip 1.4mm, at 60" MS 2+ 2.5 at 100°C after 10 pass by open roll, nip 1.4mm, at 50°C. 2) Solution viscosity : 10% in Toluene solution by BF type viscometer at 20°C 2. Test Formulation DENKA CR Antioxidant BHT Magnesia 430 Zine oxide No.2 BP. resin 1634 Solvent Toluene « prereaction 6hrs at 23°C 3. Adhesion Test 1) Initial bonding strength peel strength by cotton canvas open time 30min. set time Shrs. at 23°C 180degree T type peel 50mm/min. at 23°C 2) Final bonding strength peel strength by cotton canvas, ‘open time 30min. set time 10days at 23°C 180degree T type peel 50mm/min. at 23°C 3) Bonding strength at elevated temperature peel strength by cotton canvas open time 30min. set time 10days at 23°C 180degree T type peel 50mm/min. at 60°C 4) Tack retention time peel strength by cotton canvas open time various, set time 5days at 23°C. 180degree T type peel 50mm/min. at 23°C [COMMENTS] This description gives the detailed test methods applied in Table~2. The detail of the prereaction of MgO/t-BP resin/solvent is reported separately.Table 3 Basic Properties of [ A-30] General Characteristics of A~30 Ronearance White or light colored Mooney viscosity (MS 2425 100°C) 20 +k 3 Volatile matter ‘Less than 1.0% (wt) Specific gravity 123 + 003 Orysterlization rate Fast Grade A-30 A-30 A-90 A-90 Test Item Process Direct dissolving Milled Polymer mooney viscosity (MS 2+25 100C)| 203 [ 48:4 | 484 | abt. 20 Roll milling time (min. at 50°O, nip:1.4mm) non non non 30 Adhesive viscosity (mPars at 25°C) 400 400 2800 400 Solid content () 250 | 155 250 | 250 ‘Spinning distanos (om) 50 30. 30 45 Degree of splach point good | (good | good | good Particle size small | llerge | large | _ small ‘Spread width (om) 25 20 21 26 ‘Spray amount (co/min) 180 225 87 200) Total Properties Balance Excellent | (Good [ Poor | Excellent Good Spinability Good Poor Good Poor Extention pattern Particle size Sprayabi lity [COMMENTS] % For the application to large surface in automated process, spray type adhesive is usually adopted. # A-80, a low viscosity grade GR is preferable es spray type adhesive, which requires low viscosity ‘end high solid content. ¥ Sprayabilty of A-30 is excellent even direct dissolution process is applied,Table-4_ Formulation of Spray Type Adhesive 1. Formulation NKA CR A-90. DENKA CR _M-130L [| Brest dssovng | ___Miled DENK CR_A-30—_] DENKA CR_M-40 ‘Antioxidant BHT Magnesia MeO #150 Zine Oxide ZnO No.2. Silica Silene EF. EButyl Phenolic_Resintt 2. Properties Solution Viscosity (mPa-s) Solid content (%) 12s required (vis. 300~1,000mPa-s) 300~800mPa:s about 22~25 % Bonding Strength [N/om” Veneer/Veneer shearing Open. Tims=30min] Set Time Temp. Initial The 25°C Final 1Odays 25°C Heat-1 days 60°C Heat-2 1Odays 80S Bonding Strength [N/om* Formica/Veneer shearing Open.Tims= Set Time Temp. the 25° Wdays 25°C Wdays 60°C 1Wdays 80°C Softening point Sprayabilty Stabirity of Solution Viscosity Phasing Stability NOTE: * 2 BP Rosin 50 substrate break 180 98 18 substrate break 180 69 150°CRLE Good Good Good Pre-Reaction —-Mgo/tBP resin/Tol. BEG hrs at 25°C for example) TAMANOL~526,CKR-1634,SP—134,FR-551 ve: Solvent system — EAG/n-Hex./Tol. = 45% / 40% / 15% (by wt) [COMMENTS] % Model formulations and adhesive properties for A-30 in direct dissolution process are shown. % These formulations are applied in construction, foot-wear and car-industry.Basic Properties of [ A-400] “Appearance, White or light colored chips 5% Solution Viscosity 500~1500 mPa:s at 20°C [_Volatile Matter less than 1,0% ( ‘Specific Gravity 4.23 & 0.03 : Crystallization Rate Fast Table 1 Adhesive Properties of A~400 TEST ITEM Raw Polymer Moony Vis(MS 2-25 at 100% HIGH |__48_ ‘Compound Mooney Vis. (MS 242.5 at 100°C) 70 | 36 | Solution Viscosity (mPa-s) i CONTROL at 5000 mPa:s ‘Solid Content (% ) I 2 [2 Open time Set time Temp. Initial * 30 min. 10 min. __23°C Initial ¥ 30 min, 3 hrs. 30min. 5 hrs. tT day 5 days 10 days TO days: 31 10 days 22) Softening Point CO) 35) Tack Retention Time (hr) i pat Phasing Stabiity Note : Formulation DENKA CR 100 : Antioxidant (N-SP) 2 - 4 Zinc Oxide (No.2) 5 Resin (CKR-1634) 20 Toluene as required (vis. 5000mPa-s) COMMENTS) %A~400 has the highest solution viscosity among all the DENKA Chloroprene grades. #A-400, due to the very high viscosity, is not used alone, but usually blended with other grades. By blending with A-400, A-90 based adhesive gives Diower cost, @higher initial bonding strength, @improved high temperature strength.Fig. 3 Blend Properties of [ A-400 ] and [ A-90 ] 28 2 26 Solid content (%) Fy 2 09 03. 07 Peel strengths 05 04 03 02 12 " Peel strength 10 (N/mm) as 20 Peel strength2s (N/mm) 20 Solid Content SP i =< a 25778 30/70 Blend ratio A~400/A-90 Initial Bonding Strength Blend ratio A~400/A-90 Final Bonding Strength —=—— T I — 28775 30770 —¢ 25/15 30/70 Blend ratio A~400/A-90 ing Strength at 60°C Blend ratio A~400/A-80 25/75 30/70,Table-6 Basic Properties [ A-91 ] General Characteistics of A-91 JAppearance White or light colored chips } | Mooney Viscosity (MS 2+2.6 100°C) 48 + 4 | j Volatile Matter 1.0% (wt) }LR i 1 Specific Gravity 1.23 + 0.03 : | _Gosstalization ete Bd TETS ITEM GRADE Aol A-90 Raw Polymer Moony Vis (MS 2*25 at 100°C) ® a7 Compound Mooney Vie. (MS 242.6 at 100°C) 36 35 ‘Adhesive Solution Viscosity (mPavs) 10800, 10200 Adhesive Solid Content _(%) Controled at 25% Pot Life (min , gum stock with Isocyanate) 5 250 Initial Bonding Strength (N/mm , gum stock) 1 08 Initial Heat Strength (ke/In , with Isocyanate) 24 15 Other Contact Adhesion Properties A-SOIS AIC = Sa POT LIFE ieee wai a ea 2 25000 Ate 20000 A # 15000 # 10000 ® 5000 5 | ° 0100, 30200 200380 ection Fone & Pt Se (i) NOTE: Adhesive Formulation Pot Life DENKA GR 100 Initial vis. X 2 time vis. Antioxidant SF 2 o- @ Mgo #30 4 ZnO #2 5 Toluene 333 Isocyanate RFE 13.8 (i451 * A-91 has higher reactivity with isocyanate compared with A-90. ‘% Two-component adhesives reacted with isocyanate are often used in footwear and conveyor belt applications. * In order to improve the initial, final and high temperature bonding strength of two-component adhesive, choice of A-91 is most perferred because of its fast reactivity with isocyanate. aaTable-7 Formulation of Two-Component Adhesive [for Gonveyer Belt J 1. Formulation DENKA CR A-91 DENKA CR A-90 Antioxidant BHT Mognesia MgO #150 Zine Oxide _2n0 No2 Silica S02 _Nippsi-VN3 Rosin Ester Resin Estergum-H t-Butyl Phenolic Resin SP-134 Solvent. Tol./n-Hex (6/4 wt) Hardner Desmo.-RE 2. Properties Solution Viscosity (mPa:s) Solid content (8) Bonding Strength ( kg/In, SBR conveyer belt ) non buff buff (#120 emery cloth) Pot Life (min) Tack Time (min) [Recommend] [Ref] 100 100 = = = 100 2 2 2 4 4 4 5 5 5 5 5 5 10 10 40 - 10 10 401 400 400 5 phAdhesive 5000 81005100 24 25.3 25.4 1.24 1.64 068 3.55 53 331 125 15 240 90 120 125 NOTE: Effect of Resin Type for Isocyanate Reaction-speed. 25000 20000 | —— 3 Rovin trpe cae Retin exter £ $1000 8 000 3 8 o o 100 200 300 400 Reaction time(min) [COMMENTS] ‘* Choice of tackifier (resin) is important becacuse the reactivity with isocyanate is different by the grade. saaFig-4 Basic Properties of [ DCR-11 ] General Characteristics of DCR-11 r "White or light colored chips ~ J Mooney Viscosity (ML 1#4 100°C) More than 80 j Volatile Matter Less than 1.0%(wt) 1 Specific Gravity 1.23 + 0.03 ! iedium ith gol, € 100000 £ 3 8 2 S g 3 10000 8 1000 4 1 i) 100 Rotation Speed of Viscosmeter Rotor (rpm) Wall-Pane! Sealant-gun Brush Type Mastic Type ee ad [COMMENTS] % DGR-I1 contains gel (precrosslinked polymer) %* DCR-11, with its higly thixotropic property, shows completely different rheological behavior * DCR-I1, with its higly thixotropic property, is most preferred for mastic-type adhesives 4e=Table-8 Formulation for Mastics TEST ITEM DENKA OR DCR-11 Part-I DENKA CR A-90 Solvent _(Tofuene) “Terpene phenolic resin (Durez 12603) Part-I Goumarone Indene resin Solvent _ (Toluene) Lith calcium carbonate Hard Clay Part-I Magne sia (MgO #150) Zire oxide (ZnO #2) Solvent__(Toluene) Solid Content (¥) 05 wpm Solution Viscosity 1.0 rom (x 10°mPars, 25°C, 25 pm spindle : No.7 50 rpm 100 rpm 200 rpm Thixotropie Index ( Vis. T rpm 710 rpm) Extrusion Speed ( JIS‘A=1489, seo 20°C) ‘Slump Resistance ( JIS A-1439 , mm or seo/100m Geramio/ Wood ST. taay 8, 80day Slate / Wood S.7. tday ‘S.T. 30day Glass / Wood S.T. 1day ‘ST. 30day Wood / Wood ST. iday Bonding Strength ‘ST. 30day (ke/om*) Formica / Wood S.T. 1day - ST. 30day_ Alumi.” / Wood ST. 1day ST. 30day_ Slate / Slate S.T. {day ST. 30day Original Stability of after 2 month at 26°C Solution 10pm Viscosity after 8 month at 25°C t rpm (10° x mPars) 10 rpm after 4 month at 25°C -14-Table-9 Basic Properties of [A-90S]&[DCR-16] Mooney Vis(MS) | 484 Volatilo Matter | WLF Tae Chips Appearance | Lightly color| White ‘Adhesive color | Lightly FIDBARE | Medium Fig-5 Change of Grafted Viscosity 6000 5000 F sooo g 3000 s $2000 3g 31000 0 0 1 2 3 4 5 6 Polymerization Time (hr) cR 100 Mua 50 Toluene 400 ‘CR/MMA Graft MEK 200 Formulation BPO 05 BHT 1 Polymerization tomp. 85°C Polymerization time Shrs [COMMENTS] % Colorless and transparent adhesives are preferred in footwear industry. %* A-90S and DOR-16 are the ligter colored grades of A-90. ‘* DGR-16, mainly applied in footwerar industry, shows slower graft-reactivity compared with A-90S, =i6=Photo-1 Discoloration of [A-90S] & [DGR-16] General A-90S Grafted adhesive Grafted adhesive S46—Fig-6 Basic Properties of [DCR-15L] & [DCR-15H] General Characteristics of DCR-15L and DCR-15H {” 1096Tol,Solution Viscosity (20°C) (mPa‘s) 1500-2700 “|""2710-4000 “4 | Volatile Matter Less than 1.0% (wi) (Sescte Gravy “2s eons Cr Solution Viscosity VS Cost-Performance 100000 10000 = DCR-15H rt een Hight vis & Low SO, DCR-15L. ‘Low-Cost A120 1000 100 =Low Vis. & Hight S 10% Tol. Solution viscosity (mPa-s) 20°C 10 10 [COMMENTS] 100 5% Tol. Solution Viscosity (mPa-s) 25°C the important issue. * DOR-15 series are high viscosity grades which can be directly dissolved and can give better brushability. * While A~400 is blended with lower viscosity grades, DGR-15 series can be used alone. —17-Table-10 Adhesive Properties of [DCR-15L.H] Exp No. No.1 No2 No.3 Ref.|No4 No5S Noé Ref. Formulation DENKA CR DOR-I5L | 100 75 50 0 | 100 75 50 0 DENKA GR A-90 0 0 0 mW] 0 o 0 7 DENKA CR M-190H 0 2 5 3] 0 2% 50 30 Antioxidant BHT ot er ee eat Peart ere ate Magnesia Mg0 #150 | 343 3+3 343 943/349 9+9 343 349 Zinc oxide No.2 € Midssit Wasser Wocdte fas far: Yeadue’ Jataal geaEe. +-Butyl Phenol Resin 40 40 40 40 | 60 60 60 60 Solvent Toluene 799-793-787 «641 | 779 (74 «769 «625 Solution Viscosity (mPa-s) | 9140 3070 6280 4050 | 4310 3160 3200 3010 Solid Content ¥ 15916161 191 | 18 181 182215 Brushability “WE (mm) _|31__37_ 4125 (| 35 37428 Bonding Strength Settime Shrs | 043 067 067 066 |048 068 0.73 057 iday |530 568 5.76 354/498 557 628 425 canvas/canvas Bday ]113 108 100 100] 124 119 115 105 T type peel Oday] 115 108 103 103]133 129 121 109 50mmn/min 60 | 309 384 437 303/492 589 587 434 (nen) aoc | 192 245 307 191/339 403 411 243 joo'e | 139 192 211 046 }315 344 3.79 097 Settme She [197 146 127 126|171 160 168 101 iday ]256 202 152 168/180 169 1.66 1.68 plywood/formica Sday [272 253 195 202|219 208 1.98 202 Tensile Shear 1Oday |} 297 288 223 246 |258 245 228 232 2.5mm/min so [045 O71 073 036] 071 088 079 0.62 (Mpa) 80 | O10 015 012 006 | 034 096 027 0.16 10O'C 1004 006 0.05 0.02 | 0.08 012 010 0.03 Tack Retention Time (rs)| 12 14 16 14) 6 10 14 10 ity Original] 3140 9070 4230 060] 3310 3160 3200 010 60's 2week| 2960 3020 3040 3010| 3190 3150 3470 3020 60's 4 week | 3060 3260 3400 3060| 9520 3690 4910 3220 60c 6 week} 2950 3300 3400 3060] 3710 3860 4760 3460 e0'c Bweek| 3140 2680 3840 3100| 4390 4860 5920 3620 ~18-Table 11 Basic Properties of DCR-25 10000 10% Solution Viscosity [mPa-s] at 20°C J Rppearance ~~~“ [ White or light colored chips J {10% Solution Viscosity | 2710~5000 mPas_ ss {Volatile Matter _~}ikess than 1.0% (wt) j Sveciic Gravity 1,230.03 ; a Snystelization a MOG se eaee re ee ek Solution Viscosity of DCR-25 and M-Type | DGR-25 M-130H 1000 E1301 Fuso | 100 10 100 5% Solution Viscosity [mPa-s] at 20°C —19-— 1000