US 2016025 1798A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0251798 A1 Van ROSSum et al. (43) Pub. Date: Sep. 1, 2016

(54) BONDINGAGENTS FOR PLASTSOLS Publication Classification CONTAINING DOTP OR DINCH (51) Int. Cl. (71) Applicant: Eastman Chemical Company, D6N3/00 (2006.01) Kingsport, TN (US) D6N3/06 (2006.01) (52) U.S. Cl. (72) Inventors: Ruud van Rossum, Vrouwenpolder CPC ...... D06N3/0059 (2013.01): D06N3/06 (NL); Cornelis Johannes Gerardus (2013.01): D06.N3/0077 (2013.01): D06N Maria Hermans, Heinkenszand (NL); 2203/048 (2013.01): D06N2201/02 (2013.01); Daniel Henry Bolton, Kingsport, TN D06N2201/0263 (2013.01) (US) (73) Assignee: Eastman Chemical Company, (57) ABSTRACT Kingsport, TN (US) A bonding composition for adhering PVC to fabric is dis (21) Appl. No.: 14/632,528 closed. The bonding composition contains isocyanurate and organophosphate at an organophosphate to isocyanurate (22) Filed: Feb. 26, 2015 weight ratio of 4:1 to 10:1. Patent Application Publication Sep. 1, 2016 Sheet 1 of 2 US 2016/025 1798 A1

Patent Application Publication Sep. 1, 2016 Sheet 2 of 2 US 2016/025 1798 A1

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US 2016/025 1798 A1 Sep. 1, 2016

BONDINGAGENTS FOR PLASTSOLS fabric. The composition comprises (a) isocyanurate and (b) CONTAINING DOTP OR DINCH organophosphate at an organophosphate to isocyanurate weight ratio of 4:1 to 10:1. FIELD OF THE INVENTION 0013. In another aspect, the present invention provides a coating composition. The coating composition comprises: 0001. The invention generally relates to compositions for 0014 (a) a plastisol comprising pow bonding flexible PVC to synthetic fabric and to their use. der dispersed in a comprising dioctyl terephthalate or 1.2-cyclohexane dicarboxylic acid diisononyl ester; and BACKGROUND OF THE INVENTION 00.15 (b) the bonding composition according to the inven 0002 There are many applications for polyvinyl chloride tion. (PVC) coated fabrics. These include tarpaulins, conveyor 0016. In yet another aspect, the present invention provides belts, geomembranes, marquees, roofing and cladding mate a process for coating a fabric. The process comprises: rials, protective clothing, floor coverings, and many others. 0017 (a) combining the bonding composition according Historically, natural fabrics were used in these applications, to the invention with a plastisol comprising polyvinyl chlo but the natural fabrics have now been substituted, in many ride powder dispersed in a plasticizer comprising dioctyl instances, with synthetic fibers. Compared to natural fibers, terephthalate or 1.2-cyclohexane dicarboxylic acid synthetic fibers have been found to offer improved strength, disononyl ester, and toughness, lightness, moisture resistance, resistance to 0018 (b) coating at least one side of a fabric with the microorganisms, and flexibility. mixture from step (a). 0003) Synthetic fibers, however, generally have smooth 0019. The present invention also provides for articles of monofilaments. PVC coatings tend to have poor mechanical manufacture comprising a fabric coated with the coating adhesion to Smooth Surfaces. To improve adhesion, a specific composition according to the invention. bonding agent can be added to the PVC coating Solution (often a plastisol) just prior to application. The bonding agent BRIEF DESCRIPTION OF THE DRAWINGS chemically bonds with the reactive groups of the fabric and 0020 FIG. 1 is a bar graph of the peel strength of various allows the PVC coating to adhere to the fabric. PVC formulations based on DINP plasticizer from Example 0004 Most bonding agents incorporate isocyanates. A 3. class of isocyanates is called isocyanurate. 0021 FIG. 2 is a bar graph of the peel strength of various 0005. It is common to incorporate into the bonding com PVC formulations based on DOTP plasticizer from Example position an ortho- carrier, for instance, dibutyl 4. phthalate, dioctyl phthalate, or (DINP). However, even though using ortho-phthalate carriers is com DETAILED DESCRIPTION OF THE INVENTION mon, such use is often undesirable due to public opinion on 0022. It has been found, Surprisingly, that organophos the adverse health effect of . phates can improve the compatibility of bonding agents con 0006 Recently, there has been a movement away from taining isocyanurates with plastisols containing non-ortho using ortho-phthalate . phthalate plasticizers. 0007 Alternatives to ortho-phthalate plasticizers include 0023 Thus, in one aspect, the present invention provides a dioctyl terephthalate (DOTP) (also known as diethylhexyl bonding composition for adhering polyvinyl chloride to fab terephthalate (DENT)), 1.2-cyclohexane dicarboxylic acid ric. The composition comprises: disononyl ester (DINCH), hydrogenated dioctyl phthalate 0024 (a) isocyanurate; and (DHEH), hydrogenated DOTP (DOCH), citrates, Mesa 0025 (b) organophosphate, mollR (alkylsulfonic acid ester with phenol), butyloctyl 0026 wherein the weight ratio of organophosphate to iso terephthalate (BOTP), and isononylbenzoate (INB). cyanurate ranges from 4:1 to 10:1. 0008. However, commercially available bonding agents 0027. The isocyanurate preferably comprises aromatic can show poor compatibility with ortho-phthalate free plas diisocyanate groups, such as 2,4-diisocyanatotoluene, 2.6- tisols. Poor compatibility can result in a very short pot life due diisocyanatotoluene, or mixtures thereof. In one embodi to rapidly increasing plastisol viscosity and gelation of the ment, the isocyanurate comprises 2,4-toluene diisocyanate plastisol shortly after adding the bonding agent. trimer (CAS #26603-7). 0009. Thus, there is a need for a bonding agent that shows 0028 Bonding agents containing isocyanurate are com good compatibility with ortho-phthalate free PVC plastisols. mercially available. Alternatively, the isocyanurate may be There is also a need for a bonding agent that, in addition to prepared by methods using catalysts known in the art. For showing good compatibility with ortho-phthalate free PVC example, isocyanurates can be produced by oligomerization, plastisols, can improve the adherence of the PVC to fabric, in particular trimerization, from diisocyanates. The diisocy especially synthetic fabric. anates normally used for this purpose include the isomeric 0010. The present invention addresses these needs as well diisocyanatotoluenes (TDI), composed mainly of 2,4-diiso as others, which will become apparent from the following cyanatotoluene (2,4-TDI) and 2,6-diisocyanatotoluene (2,6- description and the appended claims. TDI). These can easily be converted almost completely to isocyanurates. The isocyanurate may also be produced exclu SUMMARY OF THE INVENTION sively from 2,4-TDI. 0029. The isocyanurate may be prepared by treating the 0011 The invention is as set forth in the appended claims. toluene diisocyanate, either alone or in a suitable solvent, 0012 Briefly, in one aspect, the present invention provides with a basic catalyst Such as an aliphatic tertiary amine, a a bonding composition for adhering polyvinyl chloride to basic metallic compound Such as an alkali or alkaline earth US 2016/025 1798 A1 Sep. 1, 2016

metal oxide, hydroxide carbonate, alcoholate or phenate, an carbon atoms. Specific examples of Suitable organophos alkali metal salt of an enolizable compound or a metallic salt phates include tri-ethylhexyl phosphate, tricresyl phosphate, of a weak organic carboxylic acid. Co-catalysts may be used, isodecyl diphenyl phosphate, 2-ethylhexyl diphenyl phos Such as, for example, mono-N-Substituted carbamic esters in phate, or mixtures thereof. In one embodiment, the organo conjunction with basic metallic compounds. Catalysts con phosphate comprises tri-ethylhexyl phosphate. taining metallic salts of weak organic carboxylic acids, 0035. The amount of organophosphate in the bonding optionally in the presence of a mono-N-Substituted carbamic composition may range from 50 to 99.5% by weight, based on ester, can considerably reduce polymerization times. the total weight of the bonding composition. Other amounts 0030) Suitable solvents for preparing the isocyanurate of the organophosphate are possible. Such as from 75 to include Solvents that are inert towards isocyanates, and 99.5% by weight, 80 to 99.5% by weight, 85 to 99.5% by include, for example, esters such as ethyl acetate, butyl weight, 50 to 95% by weight, 75 to 95% by weight, 80 to 95% acetate, amyl acetate, diethyl phthalate, the acetate of the by weight, 85 to 95% by weight, 50 to 92% by weight, 75 to monoethyl ether of ethylene glycol, dimethyl phthalate, and 92% by weight, 80 to 92% by weight, 85 to 92% by weight, 50 butylbenzoate: ketones such as methyl isobutyl ketone; chlo to 90% by weight, 75 to 90% by weight, 80 to 90% by weight, roform; benzene: toluene; xylene; sulfur dioxide; butyrolac or 85 to 90% by weight. tone; monochlorobenzene; o-dichlorobenzene; ethers; or 0036. The weight ratio of organophosphate to isocyanu mixtures of Such solvents. rate in the bonding composition ranges from 4:1 to 10:1. In 0031. The preparation of isocyanurate may conveniently one embodiment, the weight ratio of organophosphate to be carried out by polymerizing the toluene diisocyanate with isocyanurate ranges from 4.5:1 to 10:1. In yet other embodi a suitable catalyst until the desired polymer has been ments, the weight ratio of organophosphate to isocyanurate obtained; further polymerization may then be prevented, for ranges from 5:1 to 10:1, 6:1 to 10:1,7:1 to 10:1, 4:1 to 9:1, 5:1 example, by mechanical removal of insoluble catalysts by to 9:1, 6:1 to 9:1, or 7:1 to 9:1. filtration or by the inactivation of soluble catalysts by treat 0037. The bonding composition may also include typical ment with the calculated amount, or a slight excess thereof, of a strong acid. Such as anhydrous hydrogen chloride or phos amounts of traditional additives such as flame retardants, phoric acid. Alternatively, the toluene diisocyanate may be stabilizers, chlorinated hydrocarbons, secondary plasticizers, polymerized to a degree Such that the required polymer for Viscosity depressants, antioxidants, or mixtures thereof. mation has taken place and then after removal or inactivation 0038. The components of the bonding composition of catalyst, residual free toluene diisocyanate may be according to the invention may be combined in any known removed by Such processes as extraction, distillation, or pre manner, including simultaneously or sequentially. Heating cipitation of the polymer with a solvent in which the mono may facilitate dissolution of one or more of the components meric toluene diisocyanate is soluble. along with vigorous mixing. 0032. In addition to diisocyanates, other polyisocyanates 0039. The bonding composition of the invention is par may be used to prepare the isocyanurate polymer, for ticularly suitable as adhesion promoters for plasticized PVC example, p-phenylene diisocyanate, m-phenylene diisocyan and in particular for PVC plastisols. ate, 1-methoxyphenylene-2,4-diisocyanate, 3.3-dimethyl-4, 0040 Thus, in another aspect, the invention provides a 4'-diisocyanatodiphenylmethane, diphenylene-4,4'-diisocy coating composition. The coating composition comprises: anate, 4,4'-diisocyanatodiphenyl ether, naphthylene-1,5- 0041 (a) a plastisol comprising polyvinyl chloride (PVC) diisocyanate, hexamethylene diisocyanate, powder dispersed in a plasticizer comprising dioctyl tereph diisocyanatodicyclohexylmethane, p-xylylene diisocyanate, thalate or 1.2-cyclohexanedicarboxylic aciddisononyl ester; m-xylylene diisocyanate, isocyanatobenzyl isocyanates, 1.2, and 3,4,5,6-hexahydrodiphenylene-4,4'-diisocyanate, 4,4'-diiso 0042 (b) the bonding composition according to the inven cyanato-1,2,3,4,5,6-hexahydrodiphenylmethane, 1.2.3,4-tet tion. rahydronaphthylene-1,5-diisocyanate, toluene-2,4,6- triisocyanate, 3-methyl-4,6,4'-triisocyanato 0043. The plastisol typically contains from 20 to 150 parts diphenylmethane, 2,4,4-triisocyanatodiphenyl, 2,4,4-triso by weight of plasticizer per 100 parts of PVC powder. In one cyanato-diphenyl ether, 4,4'-diisocyanatodiphenyl methane, embodiment, the plastisol contains from 40 to 120 parts by 1-chlorophenylene-2,4-diisocyanate, and p-isocyanato ben weight of plasticizer per 100 parts of PVC powder. Zylisocyanate. 0044. In one embodiment, the plasticizer is dioctyl tereph 0033. The amount of isocyanurate in the bonding compo thalate. sition may range from 0.5 to 30% by weight, based on the 0045. In addition to PVC, the plastisol may include vinyl total weight of the bonding composition. Other amounts of copolymers such as vinyl acetate or vinyl acrylate. the isocyanurate are possible, such as from 5 to 30% by 0046. The amount of the bonding composition employed weight, 8 to 30% by weight, 10 to 30% by weight, 0.5 to 25% in the coating composition can vary, depending on the desired by weight, 5 to 25% by weight, 8 to 25% by weight, 10 to 25% degree of adhesion and the isocyanurate content of the bond by weight, 0.5 to 20% by weight, 5 to 20% by weight, 8 to ing composition. For example, for a bonding composition 20% by weight, 10 to 20% by weight, 0.5 to 15% by weight, containing 25 wt % of isocyanurate, the coating composition 5 to 15% by weight, 8 to 15% by weight, or 10 to 15% by typically contains from 1 to 8 wt % of the bonding composi weight. tion. As another example, for a bonding composition contain 0034 Any organophosphate that can improve the compat ing 8 to 20 wt % of isocyanurate, the coating composition may ibility of isocyanurate with PVC plastisols containing non contain from 1 to 20% by weight of the bonding composition. ortho-phthalate plasticizers can be used in the bonding com In one embodiment, the coating composition contains from 4 position according to the invention. Such organophosphates to 20% by weight of the bonding composition. In another include those containing alkyl or aryl groups having 7 to 10 embodiment, the coating composition contains from 4 to 15% US 2016/025 1798 A1 Sep. 1, 2016

by weight of the bonding composition. The amount by weight 0.058 While attempts have been made to be precise, the of the bonding composition is based on the total weight of the numerical values and ranges described herein should be con coating composition. sidered to be approximations (even when not qualified by the 0047. The coating composition according to the invention term “about”). These values and ranges may vary from their may further comprise a variety of additives, such as flame stated numbers depending upon the desired properties sought retardants (e.g., antimony trioxide or aluminum trihydrox to be obtained by the present invention as well as the varia ide), stabilizers (including epoxy stabilizers), fillers (e.g., tions resulting from the standard deviation found in the mea calcium carbonate or dolomite), pigments (e.g., titanium Suring techniques. Moreover, the ranges described herein are dioxide, carbon black, or ultramarine blue), chlorinated intended and specifically contemplated to include all Sub hydrocarbons, plasticizers, Viscosity depressants (e.g., white ranges and values within the stated ranges. For example, a spirit or tallates), antioxidants (e.g., 2,6-di-t-butyl-4-meth range of 50 to 100 is intended to describe and include all ylphenol. 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepro values within the range including Sub-ranges Such as 60 to 90 panoic acid octadecyl ester, butylated hydroxytoluene, or and 70 to 80. octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate), UV 0059. The content of all documents cited herein, including absorbers (e.g., 2-hydroxyphenylbenzotriazole or 2-hy patents as well as non-patent literature, is hereby incorporated droxybenzophenones), biocides (e.g., 2-n-octyl-4-isothiazo by reference in their entirety. To the extent that any incorpo lin-3-one, 4.5,-dichloro-2-n-octyl-4-isothiazolin-3-one or rated Subject matter contradicts with any disclosure herein, 10,10'-oxybisphenoxarsine), or mixtures thereof. the disclosure herein shall take precedence over the incorpo 0048. The bonding agent is typically added to the plastisol, rated content. mixed at slightly elevated temperature (e.g., 20-30°C.), and 0060. This invention can be further illustrated by the fol de-aerated shortly before use. The mixed composition is par lowing examples of preferred embodiments thereof, although ticularly suitable for coating fabric, particularly fabric made it will be understood that these examples are included merely from synthetic fiber. for purposes of illustration and are not intended to limit the 0049. Thus, in another aspect, the invention provides a Scope of the invention. process for coating a fabric. The process comprises: 0050 (a) combining the bonding composition according EXAMPLES to the invention with a plastisol comprising polyvinyl chlo 0061 Table 1 shows the commercial bonding agents that ride powder dispersed in a plasticizer comprising dioctyl were tested in the examples below, where DINP is diisononyl terephthalate or 1.2-cyclohexane dicarboxylic acid phthalate, INB is isononyl benzoate, and TEHP is triethyl disononyl ester; and hexyl phosphate. 0051 (b) coating at least one side of a fabric with the mixture from Step (a). TABLE 1 0052. The fabric to be coated preferably comprises poly Isocyanate Content ester or polyamide fibers. The fabric may be coated on one or Bonding Agent Supplier (wt %) Carrier both sides using techniques known in the art, such as by spreading, dipping, or calendering on conventional equip Vulcabond MDX Akcros Chemicals 25 DINP Nourybond 289 Air Products 25 DINP ment. Nourybond 290 Air Products 30 DINP 0053. In one embodiment, the coating process further TLLXSS1099 Lanxess 25 INB comprises (c) exposing the coated fabric to elevated tempera Permuthane XR 13 Stahl Waalwijk 25 DINP 553 ture to fuse the coating. The fusing step may be carried out, for Vulcabond TP Akcros Chemicals 25 TEHP example, at a temperature of 110 to 210° C. for 30 to 90 Vulcabond TP30 Akcros Chemicals 30 TEHP seconds, until fusion is sufficiently completed. Permuthane XR22- Stahl Waalwijk 30 DINP 0054 Additional coats of the coating composition of the 556 invention, or of another PVC composition may subsequently be applied and heated in a similar fashion. 0062 Table 2 shows the plasticizers that were tested. 0055. The present invention also provides for articles of manufacture comprising a fabric coated with the coating TABLE 2 composition according to the invention. Such articles of manufacture include tarpaulins, billboards, air-supported Plasticizer Name Abbreviation structures and other textile structures, flexible containers, disononyl phthalate DINP polygonal roofs, geomembranes, pool-liners, awnings, pro dioctyl terephthalate DOTP trimethylpentanyl diisobutyrate TXIB tective apparel, conveyor belts, flock carpets, and foamed di-butyl terephthalate DBT synthetic leather. BenZoflex 9-88 B9-88 0056. The present invention includes any and all combi BenZoflex 1046 B 1046 Triacetin Triacetin nations of embodiments, features, parameters, and/or ranges 12-cyclohexane dicarboxylic acid diisononyl DINCH disclosed herein. That is, the invention may be defined by any ester combination of embodiments, features, parameters, and/or bis(2-propylheptyl) phthalate DPHP ranges described herein. 0057. As used herein, the indefinite articles “a” and “an mean one or more, unless the context clearly suggests other Example 1 wise. Similarly, the singular form of nouns includes their plural form, and Vice versa, unless the context clearly Sug 0063. To quickly determine the compatibility of the plas gests otherwise. ticizers with the commercial bonding agents and to detect US 2016/025 1798 A1 Sep. 1, 2016 visual changes, the commercial bonding agents were mixed (0070. As seen from Table 5, adding TEHP significantly directly with the plasticizers, instead of using PVC plastisols. improved the compatibility of DOTP with the bonding 0064. The mixtures were prepared by adding the plasti agents. cizer to the bonding agent in a vial at a 5:1 weight ratio of plasticizer to bonding agent, shaking the vial firmly by hand, and then observing the mixture after 24 hours. Example 3 0065. The appearance of the mixtures was rated for cloudiness, gelation, color change, and viscosity according to 0071. A plastisol was prepared by mixing the ingredients scale set forth in Table 3. shown in Table 6 at the listed proportions.

TABLE 3 TABLE 6 Rating Appearance Amount Plastisol Formulation (parts by weight) 5 Clear, colorless, easily pourable 4 Clear, slightly colored, easily pourable Plasticizer 3 Turbid, white, easily pourable 2 Some residue, easily pourable DINP 77 1 Turbid, colored, gelled Stabilizer Lankromark E2307 (ESBO) 3 0066. The appearance rating of the mixtures is reported in Lankrostab LZB 600 2 Table 4. TABLE 4

Plasticizer

Bonding Agent DNP DOTP TXIB DBT B 9-88 B 1046 Triacetin DINCH DPHP

Vulcabond MDX 5 1 nt nt nt nt nt 1 5 Nourybond 289 5 2 nt 5 nt 5 5 5 nt Nourybond 290 2 2 nt nt nt 4 2 2 nt TLLXSS1099 5 1 1 1 1 1 1 3 nt Permuthane 5 2 1 1 1 nt nt 4 5 XR13 553 Vulcabond TP 5 3 5 nt nt nt 5 5 5 Vulcabond TP30 5 5 nt nt nt nt 5 Permuthane 1 5 5 5 5 5 XR 22-556 nit = not tested

0067. As seen from Table 4, the results show that DINP TABLE 6-continued and DPHP, both ortho-phthalates, are more compatible with most of the tested bonding agents than the other plasticizers Amount tested. DOTP, in particular, showed low compatibility with Plastisol Formulation (parts by weight) most of the tested bonding agents. PVC Grade Example 2 Lacovy PB 1702 40 0068. The procedure of Example 1 was repeated with mix Westolit B7021 ultra 60 tures containing 2 parts by weight of bonding agent, 6 parts by Filler weight of DOTP as the plasticizer, and 1 part by weight of Omyacarb 5 GU 15 triethylhexyl phosphate (TEHP) as a compatibilizer. 0069. The appearance of the mixtures was rated using the Total 197 scale in Table 3 immediately after mixing as well as after 3 days. The results are reported in Table 5. 0072 Adhesive compositions were prepared by adding 2, TABLE 5 3, or 4 wt % of the bonding agent Vulcabond TP to the prepared plastisol at 30°C. The compositions were properly Plasticizer mixed and de-aerated. Vulcabond TP is a 25 wt % isocyanu DOTP DOTP rate solution mainly in a mixture of DBT (50 wt %) and TEHP Bonding Agent Compatibilizer Initial 3 Days (15 wt %). Vulcabond MDX TEHP 5 2 0073. A second bonding agent was prepared using a mix Nourybond 289 TEHP 5 5 Nourybond 290 TEHP 1 1 ture of Vulcabond TP and TEHP in a 1:1 weight ratio. The TLLXSS1099 TEHP 3 3 dosing level of this bonding agent was twice the amount of the Permuthane XR13553 TEHP 5 4 neat Vulcabond TP, since the isocyanate content was diluted Vulcabond TP TEHP 5 5 Vulcabond TP30 TEHP 5 5 to 12.5 wt % with the TEHP. Adhesive compositions were Permuthane XR22-556 TEHP 5 4 prepared by adding 4., 6, and 8 wt % of the second bonding agent to the prepared plastisol at 30° C. The compositions were properly mixed and de-aerated. US 2016/025 1798 A1 Sep. 1, 2016

0074 The adhesive compositions were then coated onto adhesive compositions from Examples 3 and 4 were moni 12 fiber threads/cmx12 fiber threads/cm sheets of polyester tored in the first 5 hours after addition of the bonding agent fiber (DEWHURST, 550 dtex) at a layer thickness of 100 and after 24 hours. g/m and placed in a Werner Mathis oven within 1 hour of I0087 A Brookfield viscosity measurement was conducted adding the bonding agent. Additional coated samples were on the plastisols at 30°C. using spindle 5, at a rotation speed prepared with adhesive compositions that were allowed to sit of 10 rpm. for 24 hours at 30° C. I0088. The viscosity results for adhesive compositions 0075. The adhesive compositions on the coated fabric from Examples 3 and 4 are shown in Tables 7 and 8, respec were fused in the oven at 190° C. for 1 minute. tively, where TP refers to Vulcabond TP and the percentages 0076. The coated fabric samples were then subjected to a of TP are by weight. 90° peel test. TABLE 7 Peel Test Procedure Viscosity Stability at 30° C. for DINP-Based PlastiSol Samples 0077. Two test pieces of coated fabric size 3x20 cm were Viscosity aftern hours at 30° C. HF welded together with the coated sides facing each other, Adhesive mPas for an area of 2x15 cm. 0078 Each loose end of the test sample was clamped in a Formulation n = 0 n = 1 n = 2 n = 3 n = 4 n = 5 n = 24 material test machine and peeled under an angle of 90 degrees Plastisol Alone 1280 1080 1180 1000 1040 1000 1080 at a speed of 100 mm/min. The average peel force was mea Plastisol + 2% TP 1200 1080 1040 1080 1280 1680 12SOOO Sured on 8 cm of the welded area, disregarding the start and Plastisol + 3% TP 1240 1080 116O 1120 132O 1560 18OOOO ending of the test. Plastisol + 4% TP 1240 1040 116O 1160 1520 1920 18OOOO Plastisol (duplo) 1440 1080 1120 1080 1120 108O 1160 0079. The force was extrapolated to N/5 cm bond width. Plastisol + 4% TP. 92O 800 840 88O 960 1080 SOOOO 0080. The peel test results are shown in FIG. 1 along with TEHP a coated Sample that was made with just the prepared plastisol Plastisol + 6% TP. 880 800 800 800 880 960 6OOOO TEHP and no bonding agent. Plastisol + 8%TP. 8OO 680 700 76O 880 880 62OOO 0081. As seen from FIG. 1, the results show a good TEHP increase in peel strength with increasing amount of bonding agent. The Vulcabond TP/TEHP 50/50 mixture results were comparable with the neat VulcabondTP results. The results of adhesive compositions that were allowed to sit for 24 hours at TABLE 8 30° C. showed little increase in peel strength, which is Viscosity Stability at 30° C. for DOTP-Based Plastisol Samples expected due to the limited pot life of the adhesive composi tion. Viscosity aftern hours at 30° C. Adhesive mPas

Example 4 Formulation n = 0 n = 1 n = 2 n = 3 n = 4 n = 5 n = 24 I0082) Example 3 was repeated except that DINP in the Plastisol Alone 1160 1000 840 880 960 880 1000 prepared plastisol was replaced with DOTP. Plastisol + 2% TP 1280 156O 1840 1840 2080 2040 4240 Plastisol + 3% TP 1600 2000 2040 2240 22OO 2440 7OOO I0083. The 90° peel test results are shown in FIG. 2 along Plastisol + 4% TP 184O 244O 232O 2400 276O 28OO 17060 with a coated Sample that was made with just the prepared Plastisol (duplo) 1160 920 92O 920 880 880 880 plastisol and no bonding agent. Plastisol + 4% TP. 960 96.O 960 1080 116O 1120 1600 TEHP 0084. As seen from FIG. 2, the results for DOTP adhesive Plastisol + 6% TP. 840 960 1080 1 120 1120 1160 2840 compositions showed good peel strength increase with TEHP increasing amount of bonding agent. The Vulcabond Plastisol + 8%TP. 8OO 1120 1560 1840 1880 1960 18640 TP/TEHP 50/50 mixture results were in line or even better TEHP compared to the neat Vulcabond TP results. Also, there was no positive adhesion effect after storage of the adhesive com 0089. As seen from Tables 7 and 8, the results show a position for 24 hours at 30°C., as expected due to the limited stable viscosity for both the DINP- and DOTP-based plasti pot life. sols without bonding agent. The adhesive compositions with 0085 Comparing the results of FIGS. 1 and 2, eventhough Vulcabond TP showed higher initial viscosity compared to the DOTP-based plastisols seemed to have lower initial peel the samples with TP/TEHP. Overall, the Vulcabond TP strength at 2 and 3 wt % loadings of neat Vulcabond TP samples showed more viscosity increase within the first 5 compared to the corresponding DINP-based samples; at 8wt hours than the samples with TP/TEHP TEHP provided a % of the Vulcabond TP/TEHP 50/50 mixture, the initial peel lower initial viscosity and better viscosity stability. strength surpassed that of the corresponding DINP-based plastisol. Example 6 Example 5 0090. A bonding agent was prepared by vacuum distilling Desmodur RC (an aromatic isocyanurate trimer product from 0.086 Besides adhesion, it is also desirable to have a more Bayer with 35 wt % of isocyanate in ethyl acetate) to remove or less constant viscosity during the pot life. Increasing vis the majority of the ethyl acetate. The ethyl acetate was cosity could have a negative effect on the penetration of the replaced with TEHP. This solution was further diluted with adhesive composition into the fiber structure of the fabric and TEHP to obtain a bonding agent containing 12.5 wt % of reduce the final peel strength. Therefore, the viscosity of the isocyanate. US 2016/025 1798 A1 Sep. 1, 2016

0091. The invention has been described in detail with par 11. The coating composition according to claim 10, ticular reference to preferred embodiments thereof, but it will wherein the plastisol further comprises vinyl copolymers. be understood that variations and modifications can be 12. The coating composition according to claim 10, which effected within the spirit and scope of the invention. comprises 4 to 15% by weight of the bonding composition, We claim: 1. Abonding composition for adhering polyvinyl chloride based on the total weight of the coating composition. to fabric, comprising: 13. The coating composition according to claim 10, which (a) isocyanurate; and comprises from 40 to 120 parts by weight of plasticizer per (b) organophosphate, 100 parts of PVC particles. wherein the weight ratio of organophosphate to isocyanu 14. The coating composition according to claim 10, rate ranges from 4:1 to 10:1. wherein the organophosphate comprises tri-ethylhexyl phos 2. The bonding composition according to claim 1, wherein phate. the isocyanurate comprises aromatic diisocyanate groups. 3. The bonding composition according to claim 1, wherein 15. The coating composition according to claim 10, which the isocyanurate comprises 2,4-toluene diisocyanate trimer. further comprises flame retardants, stabilizers, fillers, pig 4. The bonding composition according to claim 1, which ments, chlorinated hydrocarbons, secondary plasticizers, vis comprises 8 to 20% by weight of the isocyanurate, based on cosity depressants, antioxidants, UV absorbers, biocides, or the total weight of the bonding composition. mixtures thereof. 5. The bonding composition according to claim 1, wherein 16. A process for coating a fabric, comprising: the organophosphate comprises alkyl or aryl groups having 7 (a) combining the bonding composition according to claim to 10 carbon atoms. 1 with a plastisol comprising polyvinyl chloride powder 6. The bonding composition according to claim 1, wherein the organophosphate comprises tri-ethylhexyl phosphate, tri dispersed in a plasticizer comprising dioctyl terephtha cresyl phosphate, isodecyl diphenyl phosphate, 2-ethylhexyl late or 1.2-cyclohexane dicarboxylic acid diisononyl diphenyl phosphate, or mixtures thereof. ester, and 7. The bonding composition according to claim 1, wherein (b) coating at least one side of a fabric with the mixture the organophosphate comprises tri-ethylhexyl phosphate. from step (a). 8. The bonding composition according to claim 1, which 17. The process according to claim 16, wherein the plasti comprises 85 to 90% by weight of organophosphate, based on sol further comprises vinyl copolymers. the total weight of the bonding composition. 9. The bonding composition according to claim 1, wherein 18. The process according to claim 16, wherein the fabric the weight ratio of organophosphate to isocyanurate ranges comprises polyester or polyamide. from 7:1 to 9:1. 19. The process according to claim 16, which further com 10. A coating composition comprising: prises (c) exposing the coated fabric to elevated temperature (a) a plastisol comprising polyvinyl chloride (PVC) pow to fuse the coating. der dispersed in a plasticizer comprising dioctyl tereph thalate or 1.2-cyclohexane dicarboxylic acid diisononyl 20. An article of manufacture comprising a fabric coated ester, and with the coating composition according to claim 10. (b) the bonding composition according to claim 1. k k k k k