[go: up one dir, main page]

US20160251798A1 - Bonding agents for plastisols containing dotp or dinch - Google Patents

Bonding agents for plastisols containing dotp or dinch Download PDF

Info

Publication number
US20160251798A1
US20160251798A1 US14/632,528 US201514632528A US2016251798A1 US 20160251798 A1 US20160251798 A1 US 20160251798A1 US 201514632528 A US201514632528 A US 201514632528A US 2016251798 A1 US2016251798 A1 US 2016251798A1
Authority
US
United States
Prior art keywords
composition according
weight
bonding composition
organophosphate
isocyanurate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US14/632,528
Inventor
Ruud van Rossum
Cornelis Johannes Gerardus Maria Hermans
Daniel Henry Bolton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Priority to US14/632,528 priority Critical patent/US20160251798A1/en
Assigned to EASTMAN CHEMICAL MIDDELBURG B. V. reassignment EASTMAN CHEMICAL MIDDELBURG B. V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HERMANS, CORNELIS JOHANNES GERARDUS MARIA, VAN ROSSUM, Ruud
Assigned to EASTMAN CHEMICAL COMPANY reassignment EASTMAN CHEMICAL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOLTON, DANIEL HENRY
Assigned to EASTMAN CHEMICAL COMPANY reassignment EASTMAN CHEMICAL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EASTMAN CHEMICAL MIDDELBURG B.V.
Priority to EP16706115.9A priority patent/EP3262231B1/en
Priority to PCT/US2016/017055 priority patent/WO2016137738A1/en
Priority to CN201680012141.2A priority patent/CN107257834B/en
Publication of US20160251798A1 publication Critical patent/US20160251798A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/06—Homopolymers or copolymers of vinyl chloride
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0034—Polyamide fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0036—Polyester fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0263—Polyamide fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/045—Vinyl (co)polymers
    • D06N2203/048—Polyvinylchloride (co)polymers

Definitions

  • the invention generally relates to compositions for bonding flexible PVC to synthetic fabric and to their use.
  • PVC polyvinyl chloride
  • Synthetic fibers however, generally have smooth monofilaments.
  • PVC coatings tend to have poor mechanical adhesion to smooth surfaces.
  • a specific bonding agent can be added to the PVC coating solution (often a plastisol) just prior to application. The bonding agent chemically bonds with the reactive groups of the fabric and allows the PVC coating to adhere to the fabric.
  • isocyanates A class of isocyanates is called isocyanurate.
  • ortho-phthalate carrier for instance, dibutyl phthalate, dioctyl phthalate, or diisononyl phthalate (DINP).
  • DINP diisononyl phthalate
  • ortho-phthalate plasticizers include dioctyl terephthalate (DOTP) (also known as diethylhexyl terephthalate (DENT)), 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH), hydrogenated dioctyl phthalate (DHEH), hydrogenated DOTP (DOCH), citrates, Mesamoll® (alkylsulfonic acid ester with phenol), butyloctyl terephthalate (BOTP), and isononyl benzoate (INB).
  • DENT diethylhexyl terephthalate
  • DICH 1,2-cyclohexane dicarboxylic acid diisononyl ester
  • DHEH hydrogenated dioctyl phthalate
  • DOTP hydrogenated DOTP
  • citrates Mesamoll® (alkylsulfonic acid ester with phenol), butyloctyl terephthalate (BOTP
  • the present invention provides a bonding composition for adhering polyvinyl chloride to fabric.
  • the composition comprises (a) isocyanurate and (b) organophosphate at an organophosphate to isocyanurate weight ratio of 4:1 to 10:1.
  • the present invention provides a coating composition.
  • the coating composition comprises:
  • a plastisol comprising polyvinyl chloride powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester;
  • the present invention provides a process for coating a fabric.
  • the process comprises:
  • step (b) coating at least one side of a fabric with the mixture from step (a).
  • the present invention also provides for articles of manufacture comprising a fabric coated with the coating composition according to the invention.
  • FIG. 1 is a bar graph of the peel strength of various PVC formulations based on DINP plasticizer from Example 3.
  • FIG. 2 is a bar graph of the peel strength of various PVC formulations based on DOTP plasticizer from Example 4.
  • organophosphates can improve the compatibility of bonding agents containing isocyanurates with plastisols containing non-ortho-phthalate plasticizers.
  • the present invention provides a bonding composition for adhering polyvinyl chloride to fabric.
  • the composition comprises:
  • organophosphate to isocyanurate ranges from 4:1 to 10:1.
  • the isocyanurate preferably comprises aromatic diisocyanate groups, such as 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, or mixtures thereof.
  • the isocyanurate comprises 2,4-toluene diisocyanate trimer (CAS #26603-7).
  • Bonding agents containing isocyanurate are commercially available.
  • the isocyanurate may be prepared by methods using catalysts known in the art.
  • isocyanurates can be produced by oligomerization, in particular trimerization, from diisocyanates.
  • the diisocyanates normally used for this purpose include the isomeric diisocyanatotoluenes (TDI), composed mainly of 2,4-diisocyanatotoluene (2,4-TDI) and 2,6-diisocyanatotoluene (2,6-TDI). These can easily be converted almost completely to isocyanurates.
  • the isocyanurate may also be produced exclusively from 2,4-TDI.
  • the isocyanurate may be prepared by treating the toluene diisocyanate, either alone or in a suitable solvent, with a basic catalyst such as an aliphatic tertiary amine, a basic metallic compound such as an alkali or alkaline earth metal oxide, hydroxide carbonate, alcoholate or phenate, an alkali metal salt of an enolizable compound or a metallic salt of a weak organic carboxylic acid.
  • a basic catalyst such as an aliphatic tertiary amine, a basic metallic compound such as an alkali or alkaline earth metal oxide, hydroxide carbonate, alcoholate or phenate, an alkali metal salt of an enolizable compound or a metallic salt of a weak organic carboxylic acid.
  • Co-catalysts may be used, such as, for example, mono-N-substituted carbamic esters in conjunction with basic metallic compounds.
  • Suitable solvents for preparing the isocyanurate include solvents that are inert towards isocyanates, and include, for example, esters such as ethyl acetate, butyl acetate, amyl acetate, diethyl phthalate, the acetate of the monoethyl ether of ethylene glycol, dimethyl phthalate, and butyl benzoate; ketones such as methyl isobutyl ketone; chloroform; benzene; toluene; xylene; sulfur dioxide; butyrolactone; monochlorobenzene; o-dichlorobenzene; ethers; or mixtures of such solvents.
  • esters such as ethyl acetate, butyl acetate, amyl acetate, diethyl phthalate, the acetate of the monoethyl ether of ethylene glycol, dimethyl phthalate, and butyl benzoate
  • ketones such as methyl is
  • the preparation of isocyanurate may conveniently be carried out by polymerizing the toluene diisocyanate with a suitable catalyst until the desired polymer has been obtained; further polymerization may then be prevented, for example, by mechanical removal of insoluble catalysts by filtration or by the inactivation of soluble catalysts by treatment with the calculated amount, or a slight excess thereof, of a strong acid, such as anhydrous hydrogen chloride or phosphoric acid.
  • a strong acid such as anhydrous hydrogen chloride or phosphoric acid.
  • the toluene diisocyanate may be polymerized to a degree such that the required polymer formation has taken place and then after removal or inactivation of catalyst, residual free toluene diisocyanate may be removed by such processes as extraction, distillation, or precipitation of the polymer with a solvent in which the monomeric toluene diisocyanate is soluble.
  • polyisocyanates may be used to prepare the isocyanurate polymer, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 3,3-dimethyl-4,4′-diisocyanatodiphenylmethane, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanatodiphenyl ether, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diisocyanatodicyclohexylmethane, p-xylylene diisocyanate, m-xylylene diisocyanate, isocyanatobenzyl isocyanates, 1,2,3,4,5,6-hexahydrodiphenylene-4,4′-diisocyanate, 4,4′-diisocyana
  • the amount of isocyanurate in the bonding composition may range from 0.5 to 30% by weight, based on the total weight of the bonding composition.
  • Other amounts of the isocyanurate are possible, such as from 5 to 30% by weight, 8 to 30% by weight, 10 to 30% by weight, 0.5 to 25% by weight, 5 to 25% by weight, 8 to 25% by weight, 10 to 25% by weight, 0.5 to 20% by weight, 5 to 20% by weight, 8 to 20% by weight, 10 to 20% by weight, 0.5 to 15% by weight, 5 to 15% by weight, 8 to 15% by weight, or 10 to 15% by weight.
  • organophosphate that can improve the compatibility of isocyanurate with PVC plastisols containing non-ortho-phthalate plasticizers can be used in the bonding composition according to the invention.
  • organophosphates include those containing alkyl or aryl groups having 7 to 10 carbon atoms.
  • suitable organophosphates include tri-ethylhexyl phosphate, tricresyl phosphate, isodecyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, or mixtures thereof.
  • the organophosphate comprises tri-ethylhexyl phosphate.
  • the amount of organophosphate in the bonding composition may range from 50 to 99.5% by weight, based on the total weight of the bonding composition.
  • Other amounts of the organophosphate are possible, such as from 75 to 99.5% by weight, 80 to 99.5% by weight, 85 to 99.5% by weight, 50 to 95% by weight, 75 to 95% by weight, 80 to 95% by weight, 85 to 95% by weight, 50 to 92% by weight, 75 to 92% by weight, 80 to 92% by weight, 85 to 92% by weight, 50 to 90% by weight, 75 to 90% by weight, 80 to 90% by weight, or 85 to 90% by weight.
  • the weight ratio of organophosphate to isocyanurate in the bonding composition ranges from 4:1 to 10:1. In one embodiment, the weight ratio of organophosphate to isocyanurate ranges from 4.5:1 to 10:1. In yet other embodiments, the weight ratio of organophosphate to isocyanurate ranges from 5:1 to 10:1, 6:1 to 10:1, 7:1 to 10:1, 4:1 to 9:1, 5:1 to 9:1, 6:1 to 9:1, or 7:1 to 9:1.
  • the bonding composition may also include typical amounts of traditional additives such as flame retardants, stabilizers, chlorinated hydrocarbons, secondary plasticizers, viscosity depressants, antioxidants, or mixtures thereof.
  • traditional additives such as flame retardants, stabilizers, chlorinated hydrocarbons, secondary plasticizers, viscosity depressants, antioxidants, or mixtures thereof.
  • the components of the bonding composition according to the invention may be combined in any known manner, including simultaneously or sequentially. Heating may facilitate dissolution of one or more of the components along with vigorous mixing.
  • the bonding composition of the invention is particularly suitable as adhesion promoters for plasticized PVC and in particular for PVC plastisols.
  • the invention provides a coating composition.
  • the coating composition comprises:
  • a plastisol comprising polyvinyl chloride (PVC) powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
  • the plastisol typically contains from 20 to 150 parts by weight of plasticizer per 100 parts of PVC powder. In one embodiment, the plastisol contains from 40 to 120 parts by weight of plasticizer per 100 parts of PVC powder.
  • the plasticizer is dioctyl terephthalate.
  • the plastisol may include vinyl copolymers such as vinyl acetate or vinyl acrylate.
  • the amount of the bonding composition employed in the coating composition can vary, depending on the desired degree of adhesion and the isocyanurate content of the bonding composition. For example, for a bonding composition containing 25 wt % of isocyanurate, the coating composition typically contains from 1 to 8 wt % of the bonding composition. As another example, for a bonding composition containing 8 to 20 wt % of isocyanurate, the coating composition may contain from 1 to 20% by weight of the bonding composition. In one embodiment, the coating composition contains from 4 to 20% by weight of the bonding composition. In another embodiment, the coating composition contains from 4 to 15% by weight of the bonding composition. The amount by weight of the bonding composition is based on the total weight of the coating composition.
  • the coating composition according to the invention may further comprise a variety of additives, such as flame retardants (e.g., antimony trioxide or aluminum trihydroxide), stabilizers (including epoxy stabilizers), fillers (e.g., calcium carbonate or dolomite), pigments (e.g., titanium dioxide, carbon black, or ultramarine blue), chlorinated hydrocarbons, plasticizers, viscosity depressants (e.g., white spirit or tallates), antioxidants (e.g., 2,6-di-t-butyl-4-methylphenol, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, butylated hydroxytoluene, or octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate), UV absorbers (e.g., 2-hydroxyphenylbenzotriazole or 2-hydroxybenzophenones), biocides (e
  • the bonding agent is typically added to the plastisol, mixed at slightly elevated temperature (e.g., 20-30° C.), and de-aerated shortly before use.
  • the mixed composition is particularly suitable for coating fabric, particularly fabric made from synthetic fiber.
  • the invention provides a process for coating a fabric.
  • the process comprises:
  • step (b) coating at least one side of a fabric with the mixture from step (a).
  • the fabric to be coated preferably comprises polyester or polyamide fibers.
  • the fabric may be coated on one or both sides using techniques known in the art, such as by spreading, dipping, or calendering on conventional equipment.
  • the coating process further comprises (c) exposing the coated fabric to elevated temperature to fuse the coating.
  • the fusing step may be carried out, for example, at a temperature of 110 to 210° C. for 30 to 90 seconds, until fusion is sufficiently completed.
  • Additional coats of the coating composition of the invention, or of another PVC composition may subsequently be applied and heated in a similar fashion.
  • the present invention also provides for articles of manufacture comprising a fabric coated with the coating composition according to the invention.
  • articles of manufacture include tarpaulins, billboards, air-supported structures and other textile structures, flexible containers, polygonal roofs, geomembranes, pool-liners, awnings, protective apparel, conveyor belts, flock carpets, and foamed synthetic leather.
  • the present invention includes any and all combinations of embodiments, features, parameters, and/or ranges disclosed herein. That is, the invention may be defined by any combination of embodiments, features, parameters, and/or ranges described herein.
  • Table 1 shows the commercial bonding agents that were tested in the examples below, where DINP is diisononyl phthalate, INB is isononyl benzoate, and TEHP is triethylhexyl phosphate.
  • Table 2 shows the plasticizers that were tested.
  • the commercial bonding agents were mixed directly with the plasticizers, instead of using PVC plastisols.
  • the mixtures were prepared by adding the plasticizer 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 1 The procedure of Example 1 was repeated with mixtures containing 2 parts by weight of bonding agent, 6 parts by weight of DOTP as the plasticizer, and 1 part by weight of triethylhexyl phosphate (TEHP) as a compatibilizer.
  • TEHP triethylhexyl phosphate
  • a plastisol was prepared by mixing the ingredients shown in Table 6 at the listed proportions.
  • Adhesive compositions were prepared by adding 2, 3, or 4 wt % of the bonding agent Vulcabond TP to the prepared plastisol at 30° C. The compositions were properly mixed and de-aerated.
  • Vulcabond TP is a 25 wt % isocyanurate solution mainly in a mixture of DBT (50 wt %) and TEHP (15 wt %).
  • a second bonding agent was prepared using a mixture of Vulcabond TP and TEHP in a 1:1 weight ratio.
  • the dosing level of this bonding agent was twice the amount of the neat Vulcabond TP, since the isocyanate content was diluted to 12.5 wt % with the TEHP.
  • Adhesive compositions were 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.
  • the adhesive compositions were then coated onto 12 fiber threads/cm ⁇ 12 fiber threads/cm sheets of polyester fiber (DEWHURST, 550 dtex) at a layer thickness of 100 g/m 2 and placed in a Werner Mathis oven within 1 hour of adding the bonding agent. Additional coated samples were prepared with adhesive compositions that were allowed to sit for 24 hours at 30° C.
  • the adhesive compositions on the coated fabric were fused in the oven at 190° C. for 1 minute.
  • coated fabric samples were then subjected to a 90° peel test.
  • Two test pieces of coated fabric size 3 ⁇ 20 cm were HF welded together with the coated sides facing each other, for an area of 2 ⁇ 15 cm.
  • test sample Each loose end of the test sample was clamped in a material test machine and peeled under an angle of 90 degrees at a speed of 100 mm/min. The average peel force was measured on 8 cm of the welded area, disregarding the start and ending of the test.
  • the force was extrapolated to N/5 cm bond width.
  • the peel test results are shown in FIG. 1 along with a coated sample that was made with just the prepared plastisol and no bonding agent.
  • the results show a good increase in peel strength with increasing amount of bonding agent.
  • the Vulcabond TP/TEHP 50/50 mixture results were comparable with the neat Vulcabond TP results.
  • the results of adhesive compositions that were allowed to sit for 24 hours at 30° C. showed little increase in peel strength, which is expected due to the limited pot life of the adhesive composition.
  • Example 3 was repeated except that DINP in the prepared plastisol was replaced with DOTP.
  • the 90° peel test results are shown in FIG. 2 along with a coated sample that was made with just the prepared plastisol and no bonding agent.
  • the results for DOTP adhesive compositions showed good peel strength increase with increasing amount of bonding agent.
  • the Vulcabond TP/TEHP 50/50 mixture results were in line or even better compared to the neat Vulcabond TP results. Also, there was no positive adhesion effect after storage of the adhesive composition for 24 hours at 30° C., as expected due to the limited pot life.
  • the results show a stable viscosity for both the DINP- and DOTP-based plastisols without bonding agent.
  • the adhesive compositions with Vulcabond TP showed higher initial viscosity compared to the samples with TP/TEHP.
  • the Vulcabond TP samples showed more viscosity increase within the first 5 hours than the samples with TP/TEHP.
  • TEHP provided a lower initial viscosity and better viscosity stability.
  • a bonding agent was prepared by vacuum distilling Desmodur RC (an aromatic isocyanurate trimer product from Bayer with 35 wt % of isocyanate in ethyl acetate) to remove the majority of the ethyl acetate.
  • the ethyl acetate was replaced with TEHP.
  • This solution was further diluted with TEHP to obtain a bonding agent containing 12.5 wt % of isocyanate.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

A bonding composition for adhering PVC to fabric is disclosed. The bonding composition contains isocyanurate and organophosphate at an organophosphate to isocyanurate weight ratio of 4:1 to 10:1.

Description

    FIELD OF THE INVENTION
  • The invention generally relates to compositions for bonding flexible PVC to synthetic fabric and to their use.
    • BACKGROUND OF THE INVENTION
  • There are many applications for polyvinyl chloride (PVC) coated fabrics. These include tarpaulins, conveyor belts, geomembranes, marquees, roofing and cladding materials, protective clothing, floor coverings, and many others. Historically, natural fabrics were used in these applications, but the natural fabrics have now been substituted, in many instances, with synthetic fibers. Compared to natural fibers, synthetic fibers have been found to offer improved strength, toughness, lightness, moisture resistance, resistance to microorganisms, and flexibility.
  • Synthetic fibers, however, generally have smooth monofilaments. PVC coatings tend to have poor mechanical adhesion to smooth surfaces. To improve adhesion, a specific bonding agent can be added to the PVC coating solution (often a plastisol) just prior to application. The bonding agent chemically bonds with the reactive groups of the fabric and allows the PVC coating to adhere to the fabric.
  • Most bonding agents incorporate isocyanates. A class of isocyanates is called isocyanurate.
  • It is common to incorporate into the bonding composition an ortho-phthalate carrier, for instance, dibutyl phthalate, dioctyl phthalate, or diisononyl phthalate (DINP). However, even though using ortho-phthalate carriers is common, such use is often undesirable due to public opinion on the adverse health effect of phthalates.
  • Recently, there has been a movement away from using ortho-phthalate plasticizers.
  • Alternatives to ortho-phthalate plasticizers include dioctyl terephthalate (DOTP) (also known as diethylhexyl terephthalate (DENT)), 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH), hydrogenated dioctyl phthalate (DHEH), hydrogenated DOTP (DOCH), citrates, Mesamoll® (alkylsulfonic acid ester with phenol), butyloctyl terephthalate (BOTP), and isononyl benzoate (INB).
  • However, commercially available bonding agents can show poor compatibility with ortho-phthalate free plastisols. Poor compatibility can result in a very short pot life due to rapidly increasing plastisol viscosity and gelation of the plastisol shortly after adding the bonding agent.
  • Thus, there is a need for a bonding agent that shows good compatibility with ortho-phthalate free PVC plastisols. There is also a need for a bonding agent that, in addition to showing good compatibility with ortho-phthalate free PVC plastisols, can improve the adherence of the PVC to fabric, especially synthetic fabric.
  • The present invention addresses these needs as well as others, which will become apparent from the following description and the appended claims.
    • SUMMARY OF THE INVENTION
  • The invention is as set forth in the appended claims.
  • Briefly, in one aspect, the present invention provides a bonding composition for adhering polyvinyl chloride to fabric. The composition comprises (a) isocyanurate and (b) organophosphate at an organophosphate to isocyanurate weight ratio of 4:1 to 10:1.
  • In another aspect, the present invention provides a coating composition. The coating composition comprises:
  • (a) a plastisol comprising polyvinyl chloride powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
  • (b) the bonding composition according to the invention.
  • In yet another aspect, the present invention provides a process for coating a fabric. The process comprises:
  • (a) combining the bonding composition according to the invention with a plastisol comprising polyvinyl chloride powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
  • (b) coating at least one side of a fabric with the mixture from step (a).
  • The present invention also provides for articles of manufacture comprising a fabric coated with the coating composition according to the invention.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a bar graph of the peel strength of various PVC formulations based on DINP plasticizer from Example 3.
  • FIG. 2 is a bar graph of the peel strength of various PVC formulations based on DOTP plasticizer from Example 4.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • It has been found, surprisingly, that organophosphates can improve the compatibility of bonding agents containing isocyanurates with plastisols containing non-ortho-phthalate plasticizers.
  • Thus, in one aspect, the present invention provides a bonding composition for adhering polyvinyl chloride to fabric. The composition comprises:
  • (a) isocyanurate; and
  • (b) organophosphate,
  • wherein the weight ratio of organophosphate to isocyanurate ranges from 4:1 to 10:1.
  • The isocyanurate preferably comprises aromatic diisocyanate groups, such as 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, or mixtures thereof. In one embodiment, the isocyanurate comprises 2,4-toluene diisocyanate trimer (CAS #26603-7).
  • Bonding agents containing isocyanurate are commercially available. Alternatively, the isocyanurate may be prepared by methods using catalysts known in the art. For example, isocyanurates can be produced by oligomerization, in particular trimerization, from diisocyanates. The diisocyanates normally used for this purpose include the isomeric diisocyanatotoluenes (TDI), composed mainly of 2,4-diisocyanatotoluene (2,4-TDI) and 2,6-diisocyanatotoluene (2,6-TDI). These can easily be converted almost completely to isocyanurates. The isocyanurate may also be produced exclusively from 2,4-TDI.
  • The isocyanurate may be prepared by treating the toluene diisocyanate, either alone or in a suitable solvent, with a basic catalyst such as an aliphatic tertiary amine, a basic metallic compound such as an alkali or alkaline earth metal oxide, hydroxide carbonate, alcoholate or phenate, an alkali metal salt of an enolizable compound or a metallic salt of a weak organic carboxylic acid. Co-catalysts may be used, such as, for example, mono-N-substituted carbamic esters in conjunction with basic metallic compounds. Catalysts containing metallic salts of weak organic carboxylic acids, optionally in the presence of a mono-N-substituted carbamic ester, can considerably reduce polymerization times.
  • Suitable solvents for preparing the isocyanurate include solvents that are inert towards isocyanates, and include, for example, esters such as ethyl acetate, butyl acetate, amyl acetate, diethyl phthalate, the acetate of the monoethyl ether of ethylene glycol, dimethyl phthalate, and butyl benzoate; ketones such as methyl isobutyl ketone; chloroform; benzene; toluene; xylene; sulfur dioxide; butyrolactone; monochlorobenzene; o-dichlorobenzene; ethers; or mixtures of such solvents.
  • The preparation of isocyanurate may conveniently be carried out by polymerizing the toluene diisocyanate with a suitable catalyst until the desired polymer has been obtained; further polymerization may then be prevented, for example, by mechanical removal of insoluble catalysts by filtration or by the inactivation of soluble catalysts by treatment with the calculated amount, or a slight excess thereof, of a strong acid, such as anhydrous hydrogen chloride or phosphoric acid. Alternatively, the toluene diisocyanate may be polymerized to a degree such that the required polymer formation has taken place and then after removal or inactivation of catalyst, residual free toluene diisocyanate may be removed by such processes as extraction, distillation, or precipitation of the polymer with a solvent in which the monomeric toluene diisocyanate is soluble.
  • In addition to diisocyanates, other polyisocyanates may be used to prepare the isocyanurate polymer, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 3,3-dimethyl-4,4′-diisocyanatodiphenylmethane, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanatodiphenyl ether, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diisocyanatodicyclohexylmethane, p-xylylene diisocyanate, m-xylylene diisocyanate, isocyanatobenzyl isocyanates, 1,2,3,4,5,6-hexahydrodiphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-1,2,3,4,5,6-hexahydrodiphenylmethane, 1,2,3,4-tetrahydronaphthylene-1,5-diisocyanate, toluene-2,4,6-triisocyanate, 3-methyl-4,6,4′-triisocyanato diphenylmethane, 2,4,4′-triisocyanatodiphenyl, 2,4,4′-triisocyanato-diphenyl ether, 4,4′-diisocyanatodiphenyl methane, 1-chlorophenylene-2,4-diisocyanate, and p-isocyanato benzyl isocyanate.
  • The amount of isocyanurate in the bonding composition may range from 0.5 to 30% by weight, based on the total weight of the bonding composition. Other amounts of the isocyanurate are possible, such as from 5 to 30% by weight, 8 to 30% by weight, 10 to 30% by weight, 0.5 to 25% by weight, 5 to 25% by weight, 8 to 25% by weight, 10 to 25% by weight, 0.5 to 20% by weight, 5 to 20% by weight, 8 to 20% by weight, 10 to 20% by weight, 0.5 to 15% by weight, 5 to 15% by weight, 8 to 15% by weight, or 10 to 15% by weight.
  • Any organophosphate that can improve the compatibility of isocyanurate with PVC plastisols containing non-ortho-phthalate plasticizers can be used in the bonding composition according to the invention. Such organophosphates include those containing alkyl or aryl groups having 7 to 10 carbon atoms. Specific examples of suitable organophosphates include tri-ethylhexyl phosphate, tricresyl phosphate, isodecyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, or mixtures thereof. In one embodiment, the organophosphate comprises tri-ethylhexyl phosphate.
  • The amount of organophosphate in the bonding composition may range from 50 to 99.5% by weight, based on the total weight of the bonding composition. Other amounts of the organophosphate are possible, such as from 75 to 99.5% by weight, 80 to 99.5% by weight, 85 to 99.5% by weight, 50 to 95% by weight, 75 to 95% by weight, 80 to 95% by weight, 85 to 95% by weight, 50 to 92% by weight, 75 to 92% by weight, 80 to 92% by weight, 85 to 92% by weight, 50 to 90% by weight, 75 to 90% by weight, 80 to 90% by weight, or 85 to 90% by weight.
  • The weight ratio of organophosphate to isocyanurate in the bonding composition ranges from 4:1 to 10:1. In one embodiment, the weight ratio of organophosphate to isocyanurate ranges from 4.5:1 to 10:1. In yet other embodiments, the weight ratio of organophosphate to isocyanurate ranges from 5:1 to 10:1, 6:1 to 10:1, 7:1 to 10:1, 4:1 to 9:1, 5:1 to 9:1, 6:1 to 9:1, or 7:1 to 9:1.
  • The bonding composition may also include typical amounts of traditional additives such as flame retardants, stabilizers, chlorinated hydrocarbons, secondary plasticizers, viscosity depressants, antioxidants, or mixtures thereof.
  • The components of the bonding composition according to the invention may be combined in any known manner, including simultaneously or sequentially. Heating may facilitate dissolution of one or more of the components along with vigorous mixing.
  • The bonding composition of the invention is particularly suitable as adhesion promoters for plasticized PVC and in particular for PVC plastisols.
  • Thus, in another aspect, the invention provides a coating composition. The coating composition comprises:
  • (a) a plastisol comprising polyvinyl chloride (PVC) powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
  • (b) the bonding composition according to the invention.
  • The plastisol typically contains from 20 to 150 parts by weight of plasticizer per 100 parts of PVC powder. In one embodiment, the plastisol contains from 40 to 120 parts by weight of plasticizer per 100 parts of PVC powder.
  • In one embodiment, the plasticizer is dioctyl terephthalate.
  • In addition to PVC, the plastisol may include vinyl copolymers such as vinyl acetate or vinyl acrylate.
  • The amount of the bonding composition employed in the coating composition can vary, depending on the desired degree of adhesion and the isocyanurate content of the bonding composition. For example, for a bonding composition containing 25 wt % of isocyanurate, the coating composition typically contains from 1 to 8 wt % of the bonding composition. As another example, for a bonding composition containing 8 to 20 wt % of isocyanurate, the coating composition may contain from 1 to 20% by weight of the bonding composition. In one embodiment, the coating composition contains from 4 to 20% by weight of the bonding composition. In another embodiment, the coating composition contains from 4 to 15% by weight of the bonding composition. The amount by weight of the bonding composition is based on the total weight of the coating composition.
  • The coating composition according to the invention may further comprise a variety of additives, such as flame retardants (e.g., antimony trioxide or aluminum trihydroxide), stabilizers (including epoxy stabilizers), fillers (e.g., calcium carbonate or dolomite), pigments (e.g., titanium dioxide, carbon black, or ultramarine blue), chlorinated hydrocarbons, plasticizers, viscosity depressants (e.g., white spirit or tallates), antioxidants (e.g., 2,6-di-t-butyl-4-methylphenol, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, butylated hydroxytoluene, or octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate), UV absorbers (e.g., 2-hydroxyphenylbenzotriazole or 2-hydroxybenzophenones), biocides (e.g., 2-n-octyl-4-isothiazolin-3-one, 4,5,-dichloro-2-n-octyl-4-isothiazolin-3-one or 10,10′-oxybisphenoxarsine), or mixtures thereof.
  • The bonding agent is typically added to the plastisol, mixed at slightly elevated temperature (e.g., 20-30° C.), and de-aerated shortly before use. The mixed composition is particularly suitable for coating fabric, particularly fabric made from synthetic fiber.
  • Thus, in another aspect, the invention provides a process for coating a fabric. The process comprises:
  • (a) combining the bonding composition according to the invention with a plastisol comprising polyvinyl chloride powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
  • (b) coating at least one side of a fabric with the mixture from step (a).
  • The fabric to be coated preferably comprises polyester or polyamide fibers. The fabric may be coated on one or both sides using techniques known in the art, such as by spreading, dipping, or calendering on conventional equipment.
  • In one embodiment, the coating process further comprises (c) exposing the coated fabric to elevated temperature to fuse the coating. The fusing step may be carried out, for example, at a temperature of 110 to 210° C. for 30 to 90 seconds, until fusion is sufficiently completed.
  • Additional coats of the coating composition of the invention, or of another PVC composition may subsequently be applied and heated in a similar fashion.
  • The present invention also provides for articles of manufacture comprising a fabric coated with the coating composition according to the invention. Such articles of manufacture include tarpaulins, billboards, air-supported structures and other textile structures, flexible containers, polygonal roofs, geomembranes, pool-liners, awnings, protective apparel, conveyor belts, flock carpets, and foamed synthetic leather.
  • The present invention includes any and all combinations of embodiments, features, parameters, and/or ranges disclosed herein. That is, the invention may be defined by any combination of embodiments, features, parameters, and/or ranges described herein.
  • As used herein, the indefinite articles “a” and “an” mean one or more, unless the context clearly suggests otherwise. Similarly, the singular form of nouns includes their plural form, and vice versa, unless the context clearly suggests otherwise.
  • While attempts have been made to be precise, the numerical values and ranges described herein should be considered to be approximations (even when not qualified by the term “about”). These values and ranges may vary from their stated numbers depending upon the desired properties sought to be obtained by the present invention as well as the variations resulting from the standard deviation found in the measuring techniques. Moreover, the ranges described herein are intended and specifically contemplated to include all sub-ranges and values within the stated ranges. For example, a range of 50 to 100 is intended to describe and include all values within the range including sub-ranges such as 60 to 90 and 70 to 80.
  • The content of all documents cited herein, including patents as well as non-patent literature, is hereby incorporated by reference in their entirety. To the extent that any incorporated subject matter contradicts with any disclosure herein, the disclosure herein shall take precedence over the incorporated content.
  • This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.
    • EXAMPLES
  • Table 1 shows the commercial bonding agents that were tested in the examples below, where DINP is diisononyl phthalate, INB is isononyl benzoate, and TEHP is triethylhexyl phosphate.
  • TABLE 1
    Isocyanate Content
    Bonding Agent Supplier (wt %) Carrier
    Vulcabond MDX Akcros Chemicals 25 DINP
    Nourybond 289 Air Products 25 DINP
    Nourybond 290 Air Products 30 DINP
    TL LXS 51099 Lanxess 25 INB
    Permuthane XR 13 Stahl Waalwijk 25 DINP
    553
    Vulcabond TP Akcros Chemicals 25 TEHP
    Vulcabond TP30 Akcros Chemicals 30 TEHP
    Permuthane XR 22- Stahl Waalwijk 30 DINP
    556
  • Table 2 shows the plasticizers that were tested.
  • TABLE 2
    Plasticizer Name Abbreviation
    diisononyl phthalate DINP
    dioctyl terephthalate DOTP
    trimethyl pentanyl diisobutyrate TXIB
    di-butyl terephthalate DBT
    Benzoflex 9-88 B 9-88
    Benzoflex 1046 B 1046
    Triacetin Triacetin
    1,2-cyclohexane dicarboxylic acid diisononyl DINCH
    ester
    bis(2-propylheptyl) phthalate DPHP
    • Example 1
  • To quickly determine the compatibility of the plasticizers with the commercial bonding agents and to detect visual changes, the commercial bonding agents were mixed directly with the plasticizers, instead of using PVC plastisols.
  • The mixtures were prepared by adding the plasticizer 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.
  • The appearance of the mixtures was rated for cloudiness, gelation, color change, and viscosity according to scale set forth in Table 3.
  • TABLE 3
    Rating Appearance
    5 Clear, colorless, easily pourable
    4 Clear, slightly colored, easily pourable
    3 Turbid, white, easily pourable
    2 Some residue, easily pourable
    1 Turbid, colored, gelled
  • The appearance rating of the mixtures is reported in Table 4.
  • TABLE 4
    Plasticizer
    Bonding Agent DINP DOTP TXIB DBT B 9-88 B 1046 Triacetin DINCH DPHP
    Vulcabond MDX
    5 1 n/t n/t n/t n/t n/t 1 5
    Nourybond 289 5 2 n/t 5 n/t 5 5 5 n/t
    Nourybond 290 2 2 n/t n/t n/t 4 2 2 n/t
    TL LXS 51099 5 1 1 1 1 1 1 3 n/t
    Permuthane
    5 2 1 1 1 n/t n/t 4 5
    XR 13 553
    Vulcabond TP 5 3 5 n/t n/t n/t 5 5 5
    Vulcabond TP30 5 1 5 5 n/t n/t n/t n/t 5
    Permuthane 5 1 1 5 5 5 5 5 5
    XR 22-556
    n/t = not tested
  • As seen from Table 4, the results show that DINP and DPHP, both ortho-phthalates, are more compatible with most of the tested bonding agents than the other plasticizers tested. DOTP, in particular, showed low compatibility with most of the tested bonding agents.
    • Example 2
  • The procedure of Example 1 was repeated with mixtures containing 2 parts by weight of bonding agent, 6 parts by weight of DOTP as the plasticizer, and 1 part by weight of triethylhexyl phosphate (TEHP) as a compatibilizer.
  • The appearance of the mixtures was rated using the scale in Table 3 immediately after mixing as well as after 3 days. The results are reported in Table 5.
  • TABLE 5
    Plasticizer
    DOTP DOTP
    Bonding Agent Compatibilizer Initial 3 Days
    Vulcabond MDX TEHP 5 2
    Nourybond 289 TEHP 5 5
    Nourybond 290 TEHP 1 1
    TL LXS 51099 TEHP 3 3
    Permuthane XR 13 553 TEHP 5 4
    Vulcabond TP TEHP 5 5
    Vulcabond TP30 TEHP 5 5
    Permuthane XR 22-556 TEHP 5 4
  • As seen from Table 5, adding TEHP significantly improved the compatibility of DOTP with the bonding agents.
    • Example 3
  • A plastisol was prepared by mixing the ingredients shown in Table 6 at the listed proportions.
  • TABLE 6
    Amount
    Plastisol Formulation (parts by weight)
    Plasticizer
    DINP 77
    Stabilizer
    Lankromark E2307 (ESBO) 3
    Lankrostab LZB 600 2
    PVC Grade
    Lacovyl PB 1702 40
    Vestolit B7021 ultra 60
    Filler
    Omyacarb
    5 GU 15
    Total 197
  • Adhesive compositions were prepared by adding 2, 3, or 4 wt % of the bonding agent Vulcabond TP to the prepared plastisol at 30° C. The compositions were properly mixed and de-aerated. Vulcabond TP is a 25 wt % isocyanurate solution mainly in a mixture of DBT (50 wt %) and TEHP (15 wt %).
  • A second bonding agent was prepared using a mixture of Vulcabond TP and TEHP in a 1:1 weight ratio. The dosing level of this bonding agent was twice the amount of the neat Vulcabond TP, since the isocyanate content was diluted to 12.5 wt % with the TEHP. Adhesive compositions were 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.
  • The adhesive compositions were then coated onto 12 fiber threads/cm×12 fiber threads/cm sheets of polyester fiber (DEWHURST, 550 dtex) at a layer thickness of 100 g/m2 and placed in a Werner Mathis oven within 1 hour of adding the bonding agent. Additional coated samples were prepared with adhesive compositions that were allowed to sit for 24 hours at 30° C.
  • The adhesive compositions on the coated fabric were fused in the oven at 190° C. for 1 minute.
  • The coated fabric samples were then subjected to a 90° peel test.
    • Peel Test Procedure
  • Two test pieces of coated fabric size 3×20 cm were HF welded together with the coated sides facing each other, for an area of 2×15 cm.
  • Each loose end of the test sample was clamped in a material test machine and peeled under an angle of 90 degrees at a speed of 100 mm/min. The average peel force was measured on 8 cm of the welded area, disregarding the start and ending of the test.
  • The force was extrapolated to N/5 cm bond width.
  • The peel test results are shown in FIG. 1 along with a coated sample that was made with just the prepared plastisol and no bonding agent.
  • As seen from FIG. 1, the results show a good increase in peel strength with increasing amount of bonding agent. The Vulcabond TP/TEHP 50/50 mixture results were comparable with the neat Vulcabond TP results. The results of adhesive compositions that were allowed to sit for 24 hours at 30° C. showed little increase in peel strength, which is expected due to the limited pot life of the adhesive composition.
    • Example 4
  • Example 3 was repeated except that DINP in the prepared plastisol was replaced with DOTP.
  • The 90° peel test results are shown in FIG. 2 along with a coated sample that was made with just the prepared plastisol and no bonding agent.
  • As seen from FIG. 2, the results for DOTP adhesive compositions showed good peel strength increase with increasing amount of bonding agent. The Vulcabond TP/TEHP 50/50 mixture results were in line or even better compared to the neat Vulcabond TP results. Also, there was no positive adhesion effect after storage of the adhesive composition for 24 hours at 30° C., as expected due to the limited pot life.
  • Comparing the results of FIGS. 1 and 2, even though the DOTP-based plastisols seemed to have lower initial peel strength at 2 and 3 wt % loadings of neat Vulcabond TP compared to the corresponding DINP-based samples; at 8 wt % of the Vulcabond TP/TEHP 50/50 mixture, the initial peel strength surpassed that of the corresponding DINP-based plastisol.
    • Example 5
  • Besides adhesion, it is also desirable to have a more or less constant viscosity during the pot life. Increasing viscosity could have a negative effect on the penetration of the adhesive composition into the fiber structure of the fabric and reduce the final peel strength. Therefore, the viscosity of the adhesive compositions from Examples 3 and 4 were monitored in the first 5 hours after addition of the bonding agent and after 24 hours.
  • A Brookfield viscosity measurement was conducted on the plastisols at 30° C. using spindle 5, at a rotation speed of 10 rpm.
  • The viscosity results for adhesive compositions from Examples 3 and 4 are shown in Tables 7 and 8, respectively, where TP refers to Vulcabond TP and the percentages of TP are by weight.
  • TABLE 7
    Viscosity Stability at 30° C. for DINP-Based Plastisol Samples
    Viscosity after n hours at 30° C.
    Adhesive (mPas)
    Formulation n = 0 n = 1 n = 2 n = 3 n = 4 n = 5 n = 24
    Plastisol Alone 1280 1080 1180 1000 1040 1000 1080
    Plastisol + 2% TP 1200 1080 1040 1080 1280 1680 125000
    Plastisol + 3% TP 1240 1080 1160 1120 1320 1560 180000
    Plastisol + 4% TP 1240 1040 1160 1160 1520 1920 180000
    Plastisol (duplo) 1440 1080 1120 1080 1120 1080 1160
    Plastisol + 4% TP/ 920 800 840 880 960 1080 50000
    TEHP
    Plastisol + 6% TP/ 880 800 800 800 880 960 60000
    TEHP
    Plastisol + 8% TP/ 800 680 700 760 880 880 62000
    TEHP
  • TABLE 8
    Viscosity Stability at 30° C. for DOTP-Based Plastisol Samples
    Viscosity after n hours at 30° C.
    Adhesive (mPas)
    Formulation n = 0 n = 1 n = 2 n = 3 n = 4 n = 5 n = 24
    Plastisol Alone 1160 1000 840 880 960 880 1000
    Plastisol + 2% TP 1280 1560 1840 1840 2080 2040 4240
    Plastisol + 3% TP 1600 2000 2040 2240 2200 2440 7000
    Plastisol + 4% TP 1840 2440 2320 2400 2760 2800 17060
    Plastisol (duplo) 1160 920 920 920 880 880 880
    Plastisol + 4% TP/ 960 960 960 1080 1160 1120 1600
    TEHP
    Plastisol + 6% TP/ 840 960 1080 1120 1120 1160 2840
    TEHP
    Plastisol + 8% TP/ 800 1120 1560 1840 1880 1960 18640
    TEHP
  • As seen from Tables 7 and 8, the results show a stable viscosity for both the DINP- and DOTP-based plastisols without bonding agent. The adhesive compositions with Vulcabond TP showed higher initial viscosity compared to the samples with TP/TEHP. Overall, the Vulcabond TP samples showed more viscosity increase within the first 5 hours than the samples with TP/TEHP. TEHP provided a lower initial viscosity and better viscosity stability.
    • Example 6
  • A bonding agent was prepared by vacuum distilling Desmodur RC (an aromatic isocyanurate trimer product from Bayer with 35 wt % of isocyanate in ethyl acetate) to remove the majority of the ethyl acetate. The ethyl acetate was replaced with TEHP. This solution was further diluted with TEHP to obtain a bonding agent containing 12.5 wt % of isocyanate.
  • The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (20)

We claim:
1. A bonding composition for adhering polyvinyl chloride to fabric, comprising:
(a) isocyanurate; and
(b) organophosphate,
wherein the weight ratio of organophosphate to isocyanurate ranges from 4:1 to 10:1.
2. The bonding composition according to claim 1, wherein the isocyanurate comprises aromatic diisocyanate groups.
3. The bonding composition according to claim 1, wherein the isocyanurate comprises 2,4-toluene diisocyanate trimer.
4. The bonding composition according to claim 1, which comprises 8 to 20% by weight of the isocyanurate, based on the total weight of the bonding composition.
5. The bonding composition according to claim 1, wherein the organophosphate comprises alkyl or aryl groups having 7 to 10 carbon atoms.
6. The bonding composition according to claim 1, wherein the organophosphate comprises tri-ethylhexyl phosphate, tricresyl phosphate, isodecyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, or mixtures thereof.
7. The bonding composition according to claim 1, wherein the organophosphate comprises tri-ethylhexyl phosphate.
8. The bonding composition according to claim 1, which comprises 85 to 90% by weight of organophosphate, based on the total weight of the bonding composition.
9. The bonding composition according to claim 1, wherein the weight ratio of organophosphate to isocyanurate ranges from 7:1 to 9:1.
10. A coating composition comprising:
(a) a plastisol comprising polyvinyl chloride (PVC) powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
(b) the bonding composition according to claim 1.
11. The coating composition according to claim 10, wherein the plastisol further comprises vinyl copolymers.
12. The coating composition according to claim 10, which comprises 4 to 15% by weight of the bonding composition, based on the total weight of the coating composition.
13. The coating composition according to claim 10, which comprises from 40 to 120 parts by weight of plasticizer per 100 parts of PVC particles.
14. The coating composition according to claim 10, wherein the organophosphate comprises tri-ethylhexyl phosphate.
15. The coating composition according to claim 10, which further comprises flame retardants, stabilizers, fillers, pigments, chlorinated hydrocarbons, secondary plasticizers, viscosity depressants, antioxidants, UV absorbers, biocides, or mixtures thereof.
16. A process for coating a fabric, comprising:
(a) combining the bonding composition according to claim 1 with a plastisol comprising polyvinyl chloride powder dispersed in a plasticizer comprising dioctyl terephthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester; and
(b) coating at least one side of a fabric with the mixture from step (a).
17. The process according to claim 16, wherein the plastisol further comprises vinyl copolymers.
18. The process according to claim 16, wherein the fabric comprises polyester or polyamide.
19. The process according to claim 16, which further comprises (c) exposing the coated fabric to elevated temperature to fuse the coating.
20. An article of manufacture comprising a fabric coated with the coating composition according to claim 10.
US14/632,528 2015-02-26 2015-02-26 Bonding agents for plastisols containing dotp or dinch Abandoned US20160251798A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US14/632,528 US20160251798A1 (en) 2015-02-26 2015-02-26 Bonding agents for plastisols containing dotp or dinch
EP16706115.9A EP3262231B1 (en) 2015-02-26 2016-02-09 Bonding agents for plastisols containing dotp or dinch
PCT/US2016/017055 WO2016137738A1 (en) 2015-02-26 2016-02-09 Bonding agents for plastisols containing dotp or dinch
CN201680012141.2A CN107257834B (en) 2015-02-26 2016-02-09 For adhesives containing DOTP or DINCH plastisols

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14/632,528 US20160251798A1 (en) 2015-02-26 2015-02-26 Bonding agents for plastisols containing dotp or dinch

Publications (1)

Publication Number Publication Date
US20160251798A1 true US20160251798A1 (en) 2016-09-01

Family

ID=55410272

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/632,528 Abandoned US20160251798A1 (en) 2015-02-26 2015-02-26 Bonding agents for plastisols containing dotp or dinch

Country Status (4)

Country Link
US (1) US20160251798A1 (en)
EP (1) EP3262231B1 (en)
CN (1) CN107257834B (en)
WO (1) WO2016137738A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108623770A (en) * 2017-03-22 2018-10-09 广元瑞峰新材料有限公司 The production method of PVC crosslinking accelerators
EP3909994A1 (en) * 2021-02-18 2021-11-17 LANXESS Deutschland GmbH Novel phthalate-free isocyanurate composition

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3589708T3 (en) 2017-03-01 2023-02-13 Basf Se Coating composition comprising pvc and plasticizers
CN110678524A (en) 2017-03-01 2020-01-10 巴斯夫欧洲公司 Coating agent composition comprising PVC and plasticizing component
WO2019236342A1 (en) * 2018-06-07 2019-12-12 Eastman Chemical Company Highly filled plastisols
CN109016753A (en) * 2018-06-12 2018-12-18 武汉理工大学 A kind of high crease-resistant environment-friendly PVC coating cloth and preparation method thereof of high abrasion
CN109988524B (en) * 2019-04-10 2021-06-08 福尔波西格林输送科技(中国)有限公司 Method for connecting conveying belt of rubber roller ceramic tile printing machine
FR3140629A1 (en) 2022-10-07 2024-04-12 Compagnie Generale Des Etablissements Michelin COMPOSITE COMPRISING A PLASTISOL MATRIX AND AN ADHESION PROMOTER
WO2025131813A1 (en) * 2023-12-20 2025-06-26 Lanxess Deutschland Gmbh New phthalate-free isocyanurate composition and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518729A (en) * 1980-11-05 1985-05-21 Bayer Aktiengesellschaft Solutions of isocyanato-isocyanurates in plasticizers for polyvinyl chloride, a process for their production and their use as adhesion-improving additives in coating compositions based on plasticized polyvinyl chloride
WO1995022576A1 (en) * 1994-02-16 1995-08-24 Beaver Manufacturing Company, Inc. Adhesion system
US20150232411A1 (en) * 2014-02-20 2015-08-20 Basf Se Plasticizer composition comprising di(2-ethylhexyl) terephthalate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210439A (en) * 1959-11-02 1965-10-05 Ici Ltd Coating and adhesive compositions comprising vinyl chloride polymers and polyisocyanate modified polyesters of aliphatic acids and diols with carbon:oxygen content of at least 5:2
US3505105A (en) * 1965-12-20 1970-04-07 Ici Ltd Process for coating articles with polyvinyl chloride compositions containing as bonding agent a mixture of a polyisocyanate free from isocyanurate rings and an isocyanurate polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518729A (en) * 1980-11-05 1985-05-21 Bayer Aktiengesellschaft Solutions of isocyanato-isocyanurates in plasticizers for polyvinyl chloride, a process for their production and their use as adhesion-improving additives in coating compositions based on plasticized polyvinyl chloride
WO1995022576A1 (en) * 1994-02-16 1995-08-24 Beaver Manufacturing Company, Inc. Adhesion system
US20150232411A1 (en) * 2014-02-20 2015-08-20 Basf Se Plasticizer composition comprising di(2-ethylhexyl) terephthalate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108623770A (en) * 2017-03-22 2018-10-09 广元瑞峰新材料有限公司 The production method of PVC crosslinking accelerators
EP3909994A1 (en) * 2021-02-18 2021-11-17 LANXESS Deutschland GmbH Novel phthalate-free isocyanurate composition

Also Published As

Publication number Publication date
EP3262231A1 (en) 2018-01-03
WO2016137738A1 (en) 2016-09-01
CN107257834B (en) 2019-05-21
EP3262231B1 (en) 2019-03-20
CN107257834A (en) 2017-10-17

Similar Documents

Publication Publication Date Title
EP3262231B1 (en) Bonding agents for plastisols containing dotp or dinch
JP6046324B2 (en) Phthalate-free isocyanurate preparation
KR101468826B1 (en) Phthalate-free isocyanurate formulations
US8927634B2 (en) Phthalate-free isocyanurate formulations
JP4468382B2 (en) Branched dialkyl phthalate solution of TDI isocyanurate with low monomer content and low viscosity
JP7609894B2 (en) Novel phthalate-free isocyanurate compositions and uses thereof
JPS6241278A (en) Plastisol composition
TW202542119A (en) Novel phthalate-free isocyanurate composition and use thereof
JPH0651870B2 (en) Plastisol composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: EASTMAN CHEMICAL COMPANY, TENNESSEE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BOLTON, DANIEL HENRY;REEL/FRAME:036978/0259

Effective date: 20151009

Owner name: EASTMAN CHEMICAL MIDDELBURG B. V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VAN ROSSUM, RUUD;HERMANS, CORNELIS JOHANNES GERARDUS MARIA;REEL/FRAME:036977/0756

Effective date: 20151012

AS Assignment

Owner name: EASTMAN CHEMICAL COMPANY, TENNESSEE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:EASTMAN CHEMICAL MIDDELBURG B.V.;REEL/FRAME:037163/0217

Effective date: 20151116

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION